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# Test of quantum nonlocality for cavity fields

## I Introduction

Entangled states have been at the focus of discussions in quantum information theory encompassing quantum teleportation, computing, and cryptography. Two-body entanglement  allows diverse measurement schemes which can admit tests of quantum nonlocality . Using the atom-field interaction in a high-$`Q`$ cavity we can produce quantum entanglement between cavity fields, between atoms, and between a cavity and an atom. An entangled pair of atoms have been experimentally generated using the cavity QED (Quantum electrodynamics) . The entanglement of atoms and fields in the cavity can be utilized towards a realization of the controlled-NOT gate for quantum computation .

A pair of atoms can be prepared in an entangled state using the atom-field interaction in a high-$`Q`$ cavity. The interaction of a single two-level atom with a cavity field brings about entanglement of the atom and the cavity field . If the atom does not decay into other internal states after it comes out from the cavity, the entanglement will survive for long and it can be transferred to a second atom interacting with the cavity field. The violation of Bell’s inequality can be tested by the joint measurement of atomic states.

There are proposals to entangle fields in two spatially separated cavities using the atom-field interaction . A two-level atom in its excited state passes sequentially through two resonant single-mode vacuum cavities and is found to be in its ground state after the second-cavity interaction. If the interaction with the first cavity is equivalent to a $`\pi /2`$ vacuum pulse and the second-cavity interaction is to a $`\pi `$ pulse  then the atom could have deposited a photon either in the first cavity or in the second so that the final state $`|\mathrm{\Psi }_f`$ of the two cavity field is

$$|\mathrm{\Psi }_f=\frac{1}{\sqrt{2}}(|1,0+\text{e}^{i\phi }|0,1)$$
(1)
where $`|1,0`$ denotes one photon in the first cavity and none in the second, and $`|0,1`$ vice versa. Using the entangled cavity field (1), an unknown atomic quantum state can also be teleported .

A three-level atom can act as a quantum switch to couple a vacuum cavity with the external classical coherent field. If the atom is in its intermediate state before it enters to the cavity, the AC Stark shift between the intermediate and upper-most states brings about the resonant coupling of the cavity with the external field so that the external field can be fed into the cavity. If the atom is initially in its lower-most state, the atom is unable to switch on the coupling between the cavity and the external field. Using the Ramsey interference and atomic quantum switch, Davidovich et al. suggested a coherent state entanglement $`|\mathrm{\Psi }_c`$ between two separate cavities : $`|\mathrm{\Psi }_c=B_1|\alpha ,0+B_2|0,\alpha `$, where $`|\alpha ,0`$ denotes the first cavity in the coherent state of the amplitude $`\alpha `$ and the second in the vacuum.

In this paper, we are interested in a test of nonlocality for the entangled field prepared in the spatially separated cavities. Despite the suggestions on the production of entangled cavity fields, the test of quantum entanglement, i.e., the measurement of the violation of Bell’s inequality for the entangled cavity fields has not been studied. To test quantum nonlocality, we first couple classical driving fields with the cavities where a nonlocal state is prepared. Two independent two-level atoms are then sent through respective cavities to interact off-resonantly with the cavity fields. The atomic states are measured after the interaction. Bell’s inequality can be tested by the joint probabilities of two-level atoms being in their excited or ground states. We find that quantum nonlocality can also be tested using a single atom sequentially interacting with the two cavities. We also consider potential experimental errors. The atoms normally have the Gaussian velocity distribution with the normalized standard deviation less than 5%. We show that, even with the experimental errors caused by the velocity distribution, the test can be feasible.

## II Bell’s inequality by parity measurement

It is important to choose the type of measurement variables when testing nonlocality for a given state. Banaszek and Wódkiewicz  considered even and odd parities of the field state as the measurement variables, where a state is defined to be in the even (odd) parity if the state has even (odd) numbers of photons. The even and odd parity operators, $`\widehat{O}_E`$ and $`\widehat{O}_O`$, are the projection operators to measure the probabilities of the field having even and odd numbers of photons, respectively:

$$\widehat{O}_E=\underset{n=0}{\overset{\mathrm{}}{}}|2n2n|;\widehat{O}_O=\underset{n=0}{\overset{\mathrm{}}{}}|2n+12n+1|.$$
(2)
To test the quantum nonlocality for the field state of the modes $`a`$ and $`b`$, we define the quantum correlation operator based on the joint parity measurements:

$$\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )=\widehat{\mathrm{\Pi }}_E^a(\alpha )\widehat{\mathrm{\Pi }}_E^b(\beta )\widehat{\mathrm{\Pi }}_E^a(\alpha )\widehat{\mathrm{\Pi }}_O^b(\beta )\widehat{\mathrm{\Pi }}_O^a(\alpha )\widehat{\mathrm{\Pi }}_E^b(\beta )+\widehat{\mathrm{\Pi }}_O^a(\alpha )\widehat{\mathrm{\Pi }}_O^b(\beta )$$
(3)
where the superscripts $`a`$ and $`b`$ denote the field modes and the displaced parity operator, $`\widehat{\mathrm{\Pi }}_{E,O}(\alpha )`$, is defined as

$$\widehat{\mathrm{\Pi }}_{E,O}(\alpha )=\widehat{D}(\alpha )\widehat{O}_{E,O}\widehat{D}^{}(\alpha ).$$
(4)
The displacement operator $`\widehat{D}(\alpha )`$ displaces a state by $`\alpha `$ in phase space. The displaced parity operator acts like a rotated spin projection operator in the spin measurement . We can easily derive that the local hidden variable theory imposes the following Bell’s inequality

$$|B(\alpha ,\beta )||\widehat{\mathrm{\Pi }}^{ab}(0,0)+\widehat{\mathrm{\Pi }}^{ab}(0,\beta )+\widehat{\mathrm{\Pi }}^{ab}(\alpha ,0)\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )|2$$
(5)
where we call $`B(\alpha ,\beta )`$ as the Bell function.

## III Parity measurement in cavity QED

Englert et al.  proposed an experiment to determine the parity of the field in a high-Q single-mode cavity. Let us consider a far-off resonant interaction of a two-level atom with a single-mode cavity field. If the detuning $`\mathrm{\Delta }=\omega _o\omega `$ of the atomic transition frequency $`\omega _o`$ from the cavity-field frequency $`\omega `$ is much larger than the Rabi frequency $`\mathrm{\Omega }`$, there is no energy exchange between the atom and the field but the relative phase of the atomic states changes due to the AC stark shift . The change of the phase depends on the number of photons in the cavity and on the state of the atom:

$`|e,\psi _f`$ $``$ $`\mathrm{exp}[i\mathrm{\Theta }(\widehat{n}+1)]|e,\psi _f,`$ (6)
$`|g,\psi _f`$ $``$ $`\mathrm{exp}[i\mathrm{\Theta }(\widehat{n})]|g,\psi _f`$ (7)
where the atom-field state $`|e,\psi _f`$ denotes the atom in its excited state and the cavity field in $`|\psi _f`$. The phase $`\mathrm{\Theta }(\widehat{n})`$ is a function of the number of photons in the cavity and the atom-field coupling time and strength.

If a $`\pi /2`$ pulse is applied on a two-level atom before it enters the cavity, the atom initially in its excited state transits to a superposition state without changing the cavity field

$$|e,\psi _f\frac{1}{\sqrt{2}}[|e,\psi _f+i\text{e}^{i\varphi _1}|g,\psi _f],$$
(8)
where $`\varphi _1`$ is determined by the phase of the pulse field. The atom, then, passes through a cavity and undergoes an off-resonant interaction with the cavity field where the atom-field coupling function is selected to be

$$\mathrm{\Theta }(\widehat{n})=\frac{\pi }{2}\widehat{n}.$$
(9)
After the atom comes out from the cavity, the atom is let interact with the second $`\pi /2`$ pulse. If the phases of the first and the second pulses are chosen to satisfy the following relation

$$i\text{e}^{i(\varphi _1\varphi _2)}=1,$$
(10)
the atom-field state after the second $`\pi /2`$ pulse is

$$\frac{1}{2}\left\{i[1(1)^{\widehat{n}}]|e,\psi _f+\text{e}^{i\varphi _2}[1+(1)^{\widehat{n}}]|g,\psi _f\right\}.$$
(11)
If the atom is detected in its excited state, the field has the even parity. If the atom is detected in its ground state, the field has the odd parity. The atom tells us the parity of the field .

## IV Quantum nonlocality of cavity fields

To test quantum nonlocality of the field, $`|\psi _f^{ab}`$, prepared in spatially separated two single-mode cavities, we use two two-level atoms as shown in Fig. 1(a). In this paper we assume that the mode structures of the cavities are identical and the atoms are independent identical atoms. The atoms are labelled as $`a`$ and $`b`$ to interact, respectively, with the fields in the cavities $`a`$ and $`b`$. Each atom is initially prepared in its excited state and sequentially passes through interaction zones of the first $`\pi /2`$ pulse, the cavity field, and the second $`\pi /2`$ pulse. The atoms-field state then becomes

$$|e_a,e_b|\psi _f^{ab}|\phi (\widehat{n}_a,\widehat{n}_b)|\psi _f^{ab}$$
(12)
where $`|\phi (\widehat{n}_a,\widehat{n}_b)`$ is the atomic state with the weights of the field operators ($`\widehat{n}_a`$ and $`\widehat{n}_b`$ are number operators of fields in the cavities $`a`$ and $`b`$):

$`|\phi (\widehat{n_a},\widehat{n_b})=`$ $`a(\widehat{n}_a)a(\widehat{n}_b)|e_a,e_b+a(\widehat{n}_a)b(\widehat{n}_b)|e_a,g_b`$ (13)
$`+`$ $`b(\widehat{n}_a)a(\widehat{n}_b)|g_a,e_b+b(\widehat{n}_a)b(\widehat{n}_b)|g_a,g_b`$ (14)
where $`a(\widehat{n})=[e^{i\mathrm{\Theta }(\widehat{n}+1)}e^{i(\varphi _1\varphi _2)}e^{i\mathrm{\Theta }(\widehat{n})}]/2`$ and $`b(\widehat{n})=ie^{i\varphi _2}[e^{i\mathrm{\Theta }(\widehat{n}+1)}+e^{i(\varphi _1\varphi _2)}e^{i\mathrm{\Theta }(\widehat{n})}]/2`$. Choosing appropriate conditions for the atom-field couplings and pulse phases as shown in (9) and (10), the atoms-field state becomes

$`{\displaystyle \frac{1}{4}}`$ $`\left\{i[1(1)^{\widehat{n}_a}]|e_a+\text{e}^{i\varphi _2}[1+(1)^{\widehat{n}_a}]|g_a\right\}`$ (16)
$`\times \left\{i[1(1)^{\widehat{n}_b}]|e_b+\text{e}^{i\varphi _2}[1+(1)^{\widehat{n}_b}]|g_b\right\}|\psi _f^{ab}.`$
If the atoms are jointly found in their excited states then we know that both the cavities are in the odd parity states. The joint probability $`P_{ee}`$ of the atoms being in their excited states is related to the expectation value of the following joint parity operator:

$$P_{ee}=\widehat{\mathrm{\Pi }}_O^a(0)\widehat{\mathrm{\Pi }}_O^b(0).$$
(17)
In Eqs. (3) and (5), it is seen that we need to know the joint parities of the displaced original fields to test quantum nonlocality. To displace the cavity field, external stable fields are coupled to the cavities as shown in Fig. 1(a) . After a nonlocal field state is prepared in the cavities, we couple the cavities with the external fields to displace the original nonlocal field, then send two independent atoms through respective cavities. The $`\pi /2`$ pulses shine atoms before and after the cavity interaction to provide Ramsey interference effects. The atomic states are detected after the second $`\pi /2`$ pulses. $`P_{ee}(\alpha ,\beta )`$ denotes the joint probability of atoms being in their excited states when the original fields in the cavities $`a`$ and $`b`$ are displaced by $`\alpha `$ and $`\beta `$, respectively. The expectation value of the quantum correlation operator in (3) is obtained by the joint probabilities:

$$\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )=P_{ee}(\alpha ,\beta )P_{eg}(\alpha ,\beta )P_{ge}(\alpha ,\beta )+P_{gg}(\alpha ,\beta ).$$
(18)
If there are any displacement factors $`\alpha `$ and $`\beta `$ which result in the violation of Bell’s inequality in Eq. (5), the field originally prepared in the cavities is quantum-mechanically nonlocal.

After a closer look at Eq. (3), we find that we do not need the individual parity of each cavity field to test the inequality (5). We need the parity of only the total field. Instead of sending two atoms to cavities, we now send a single two-level atom sequentially through cavities as shown in Fig. 1(b). The atom is initially prepared in its excited state and undergoes $`\pi /2`$-pulse interactions before and after the cavity interaction. The atom-field coupling strength is selected to satisfy Eq. (9) and the phases, $`\varphi _a`$ and $`\varphi _b`$, of the two $`\pi /2`$ pulses are chosen as $`\mathrm{exp}[i(\varphi _a\varphi _b)]=1`$ then the atom-field state becomes

$$|e,\psi _f^{ab}\frac{1}{2}[1+(1)^{\widehat{n}_a+\widehat{n}_b}]|e,\psi _f^{ab}+\frac{i}{2}[1(1)^{\widehat{n}_a+\widehat{n}_b}]|g,\psi _f^{ab}.$$
(19)
The external stable fields are taken to be coupled with the cavities to displace the cavity fields. The probability $`P_e(\alpha ,\beta )`$ of the atom being in its excited state after having passed displaced cavity fields and $`\pi /2`$ pulses, is the expectation value of the parity operators:

$$P_e(\alpha ,\beta )=\widehat{\mathrm{\Pi }}_O^a(\alpha )\widehat{\mathrm{\Pi }}_O^b(\beta )+\widehat{\mathrm{\Pi }}_E^a(\alpha )\widehat{\mathrm{\Pi }}_E^b(\beta )$$
(20)
where $`\alpha `$, $`\beta `$ denote the displacements of the fields in the cavities $`a`$ and $`b`$. Similarly, the probability of the atom being in its ground state $`P_g(\alpha ,\beta )`$ is found to be related to the odd parity of the total fields. The expectation value of the quantum correlation function operator in Eq. (3) is simply

$$\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )=P_e(\alpha ,\beta )P_g(\alpha ,\beta ).$$
(21)
This does not tell us the parity of each mode but the parity of the total field which is enough to test the violation of Bell’s inequality.

## V Remarks

We have suggested a simple way to test quantum nonlocality of cavity fields by measuring the states of atoms after their interaction with cavity fields. The test does not require a numerical process on the measured data. The difference in the probability of a single two-level atom being in its excited and ground states is directly related to the test of quantum nonlocality. In fact, this can also be used to reconstruct the two-mode Wigner function as the mean parity of the field is proportional to the two-mode Wigner function :

$$W(\alpha ,\beta )=(2/\pi )^2\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta ).$$
(22)
Experimental error can easily occur from the fluctuation in the atom-field coupling strength and time. The atom-field coupling function $`\mathrm{\Theta }(\widehat{n})`$ depends on the mode structure of the cavity field and on the duration of time for the atom to interact with the cavity field . Because the atomic velocity has some fluctuations the interaction time is subject to the experimental error . Another error source may be the $`\pi /2`$ pulse operation. We analyze the possibility to measure the violation of quantum nonlocality in the potential experimental situation.

The test of quantum nonlocality using the two-atom scheme in Fig. 1(a) is considered with potential experimental errors. The error in the atom-field coupling function is denoted by $`\mathrm{\Delta }\mathrm{\Theta }(\widehat{n})`$, which is the departure of the experimental value $`\mathrm{\Theta }(\widehat{n})`$ from the required value $`\mathrm{\Theta }_0(\widehat{n})`$:

$$\mathrm{\Delta }\mathrm{\Theta }(\widehat{n})=\mathrm{\Theta }(\widehat{n})\mathrm{\Theta }_0(\widehat{n})=\delta \widehat{n}$$
(23)
where $`\mathrm{\Theta }_0(\widehat{n})=(\pi /2)\widehat{n}`$. The relative phases of atomic states given by the $`\pi /2`$-pulse interactions are also subject to experimental errors. We take the phase error $`\mathrm{\Delta }\varphi `$ as

$$\mathrm{\Delta }\varphi =(\varphi _2\varphi _1)\varphi _0;i\mathrm{exp}(i\varphi _0)=1.$$
(24)
Note that the atomic state measurement is equivalent to the parity measurement as in Eq. (17) only when $`\mathrm{\Theta }(\widehat{n})=\mathrm{\Theta }_0(\widehat{n})`$ and $`\varphi _2\varphi _1=\varphi _0`$.

The errors in the atom-field coupling and phases of the $`\pi /2`$ pulses bring about the departure $`\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta )`$ of the joint atomic state probabilities from the expectation value of the parity operators in Eq. (18). The mean error of $`\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta )`$ is calculated up to the second order of $`\delta `$ and $`\mathrm{\Delta }\varphi `$ as follows

$`\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta )`$ $``$ $`P_{ee}(\alpha ,\beta )P_{eg}(\alpha ,\beta )P_{ge}(\alpha ,\beta )+P_{gg}(\alpha ,\beta )\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )`$ (25)
$`=`$ $`2\psi _f^{ab}|\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )\left[\mathrm{\Delta }(\widehat{n}_a(\alpha ))+\mathrm{\Delta }(\widehat{n}_b(\beta ))\right]|\psi ^{ab}`$ (26)
where

$$\mathrm{\Delta }(\widehat{n}_{a,b}(\alpha ))=\frac{1}{4}[2\widehat{n}_{a,b}(\alpha )+1]^2\delta ^2+\frac{1}{2}[2\widehat{n}_{a,b}(\alpha )+1]\delta \mathrm{\Delta }\varphi +\frac{1}{4}(\mathrm{\Delta }\varphi )^2$$
(27)
and $`\widehat{n}_{a,b}(\alpha )=\widehat{D}^{}(\alpha )\widehat{n}_{a,b}\widehat{D}(\alpha )`$ are the displaced number operators for the field modes in the cavities $`a`$ and $`b`$. The mean error $`\mathrm{\Delta }B(\alpha ,\beta )`$ of the Bell function measurement in (5) is given by

$$\mathrm{\Delta }B(\alpha ,\beta )=\mathrm{\Delta }\mathrm{\Pi }^{ab}(0,0)+\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,0)+\mathrm{\Delta }\mathrm{\Pi }^{ab}(0,\beta )\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta ).$$
(28)
Consider an explicit example of a quantum nonlocal field (1) for an illustration of the experimental errors. For simplicity, we take the phase factor zero, i.e., $`\phi =0`$. We know from an earlier work  that Bell’s inequality is maximally violated with $`B2.19`$ when $`\alpha =\beta `$ and $`|\alpha |^20.1`$. Substituting $`|\mathrm{\Psi }_f`$ of Eq. (1) into $`|\psi _f^{ab}`$ of Eq. (25), $`\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta )`$ is

$`\mathrm{\Delta }\mathrm{\Pi }^{ab}(\alpha ,\beta )`$ $``$ $`2\psi _f^{ab}|\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )|\psi _f^{ab}\psi _f^{ab}|\left(\mathrm{\Delta }(\widehat{n}_a(\alpha ))+\mathrm{\Delta }(\widehat{n}_b(\beta ))\right)|\psi _f^{ab}`$ (29)
$`=`$ $`2\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )\left\{c_1(\alpha ,\beta )\delta ^2+c_2(\alpha ,\beta )\delta \mathrm{\Delta }\varphi +(\mathrm{\Delta }\varphi )^2\right\}`$ (30)
where the mean field approximation has been used . The expectation value $`\widehat{\mathrm{\Pi }}^{ab}(\alpha ,\beta )=(2|\alpha \beta |^21)e^{2(|\alpha |^2+|\beta |^2)}`$, and the parameters $`c_1(\alpha ,\beta )=2(|\alpha |^4+|\beta |^4)+\frac{13}{2}(|\alpha |^2+|\beta |^2)+5`$, and $`c_2(\alpha ,\beta )=2(|\alpha |^2+|\beta |^2)+4`$. The mean error $`\mathrm{\Delta }B`$ for $`\alpha =\beta \sqrt{0.1}`$, is given by

$$\mathrm{\Delta }B10.2\delta ^2+8.1\delta \mathrm{\Delta }\varphi +2.0(\mathrm{\Delta }\varphi )^2.$$
(31)
The probing atoms normally have the Gaussian velocity distribution which causes the errors $`\delta `$ and $`\mathrm{\Delta }\varphi `$. When we consider the ensemble average over atoms, the second term vanishes in Eq. (31) and the first and third terms finally contribute to degrade the value of the Bell function.

For the test of nonlocality using single atoms as shown in Fig. 1(b), the mean error $`\mathrm{\Delta }B`$ is similarly obtained as

$$\mathrm{\Delta }B16.3\delta ^2+8.2\delta \mathrm{\Delta }\varphi +1.0(\mathrm{\Delta }\varphi )^2.$$
(32)
This is slightly larger than the error (31) for the two-atom scheme. The error enhancement in the single-atom scheme is due to the fact that the experimental errors are multiplied as the atom passes through two cavities. For the two-atom scheme, the error is a sum of errors occurred in each atom interaction with the cavity field and $`\pi /2`$ pulses.

We find that when the standard deviation of the atomic velocity distribution is 5%, $`\mathrm{\Delta }B0.06`$ for the two-atom scheme and $`\mathrm{\Delta }B0.10`$ for the single-atom scheme, which still allows the observation of the violation of Bell’s inequality.

If the $`Q`$ factor of a cavity is high, the cavity is very much closed. When an atom passes through the cavity walls the atom can lose the information on the phases of atomic states so that the scheme suggested in this paper cannot be used. However, recently, Nogues et al. suggested a way to implement $`\pi /2`$ pulses and cavity fields interactions inside the cavity . If this scheme is applied there will not be a problem of losing the $`Q`$ value to keep the atomic phase information.

###### Acknowledgements.

M.S.K. thanks Professor Walther for discussions and hospitality at the Max-Planck-Instut für Quantenoptik where a part of this work was carried out. This work was supported by the BK21 grant (D-0055) by the Korean Ministry of Education.


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# Search for molecular gas in HVCs by HCO+ absorption

## 1 Introduction

Since their discovery by Muller, Oort, & Raimond (1963), HI clouds moving with velocities that can not be explained by differential Galactic rotation (often exceeding it by 100 km s-1) have been the target of numerous surveys. Many of these high-velocity clouds (HVCs) are located at intermediate and high Galactic latitudes (Giovanelli, Verschuur, & Cram 1973; Mathewson, Schwarz, & Murray 1977; Wakker & van Woerden 1991) and do not appear to have any connection with the gas in the Galactic disk. HVCs are often found in large HI complexes with angular sizes 10–90. They cover from 10 to 37% of the sky, depending on the sensitivity of the studies (Murphy et al 1995).

The origin of HVCs is still unclear, mainly because the distances to the individual complexes are in most cases unknown. They could be cold gas corresponding to the return flow in a Galactic fountain (e.g. Houck & Bregman 1990), or gas left over from the formation of the Galaxy. Some HVCs are probably belonging to the tidal gas streams torn from the Magellanic Clouds by the Milky-Way (Mathewson et al 1974, Putman & Gibson, 1999).

Several authors have already explored the possibility that HVCs are infalling primordial gas and have associated them with the Local Group (see Wakker & van Woerden 1997 for a thorough review). Recently Blitz et al. (1999) re-examined this hypothesis, and simulating the dynamical evolution of the Local Group galaxies, used the up-to-date HI maps of HVCs to show that the HVCs are consistent with a dynamical model of infall of the ISM onto the Local group. As such, they would represent the building blocks of our galaxies in the Local group and provide fuel for star formation in the disk of the Milky Way. In their model, HVCs contain altogether 1011 M of neutral gas. From their stability analysis, they conclude that there is roughly 10 times more dark matter than luminous gas within each HVC, and that these could correspond to the mini-halos which are able to accumulate baryons, and can gather into filaments (e.g. Bond et al 1988, Babul & Rees 1992, Kepner et al 1997). HVCs would therefore be related to the hierarchical structure of the Universe (see e.g. Katz et al 1996), and to the gas seen in absorption towards quasars (Lyman-$`\alpha `$ forest and Lyman-limit lines). However, Giovanelli (1981) has pointed out that the velocity distribution of HVCs does not match that of the Local Group, but does favor an association with the Magellanic Stream, the most obvious tidal feature of the interaction between the Galaxy and the Magellanic Clouds. The discrepancy with the results from Blitz et al. (1999) comes from the fact that the latter authors have not considered all observed HVCs, but only a selection of them.

Maps of the brightest HVC complexes have revealed the existence of unresolved structure at 10 arcmin resolution, which was further resolved into high-density cloud cores at 1 arcmin resolution (Giovanelli & Haynes 1977; Wakker & Schwarz 1991; Wakker & van Woerden 1991). More generally, HVCs follow the fractal structure observed in the whole interstellar medium (Vogelaar & Wakker, 1994). The HI column densities in these cores are estimated to be several times 1020 cm-2 and their temperatures are generally between 30 and 300 K. The central densities of individual clouds can reach $`>`$ 80 cm-3 D$`{}_{}{}^{1}{}_{kpc}{}^{}`$, where Dkpc is their distance in kpc. Depending on the actual distance, which still remains poorly determined, those conditions make the HVC cores possible sites of star formation. HVCs have in fact been considered good candidates for the source of young Population I stars at large distances from the Galactic plane (see e.g. Sasselov 1993).

Attempts to measure the spin temperature of atomic hydrogen through 21cm absorption in front of background continuum sources have often only resulted in upper limits (Colgan et al. 1990, Mebold et al. 1991). A few detections have been reported (Payne et al. 1980, Wakker et al. 1991, Akeson & Blitz, 1999), with inferred spin temperature as low as 36 K, but in general most HVCs must have spin temperatures larger than 200 K or be very clumpy.

Most of our current knowledge of the gaseous content of HVCs comes from HI observations. Efforts to search for molecular hydrogen using CO emission lines have been so far unsuccessful (Wakker et al 1997), since the sub-solar metallicity and/or low density of HVCs makes direct CO emission line detection very difficult. However, optical absorption lines have shown that HVCs are not completely devoid of heavy elements (e.g. Robertson et al 1991, Lu et al 1994, Keenan et al 1995, Wakker & van Woerden 1997). The lines detected are from SiII, CII, FeII, or CIV, but the strongest are from MgII (Savage et al. 1993, Bowen & Blades 1993, Sembach et al. 1995, 1998). Metallicity studies have been done in HVCs to determine their origin. If HVCs result from the Galactic fountain effect, their metallicity should be solar while if they were associated with the Magellanic or intergalactic Clouds, it could be even less than 0.1 solar. In fact, the determined abundances are around 0.1 solar, but with much uncertainties, because of saturated lines, or dust depletion (Sembach & Savage 1996). This average metallicity is compatible with a Local-Group infall model, since X-ray observations have revealed abundances of 0.1 solar in poor groups (Davis et al 1996), and even 0.3 solar in intra-cluster gas (Renzini 1997).

If HVCs were local analogues of Lyman-limit absorbing clouds, background QSOs could enable us to detect molecules in absorption, a task which is considerably easier to achieve. Absorption has recently been reconfirmed as a very powerful tool in the millimetric range (Lucas & Liszt 1996 hereafter LL96, Combes & Wiklind 1996). A mm molecular detection would advance our knowledge of HVCs, their physical conditions, and their possible origin. A first attempt has been made in this domain by Akeson & Blitz (1999) with only negative results, using the BIMA and OVRO interferometers.

Here we report on HCO+(1-0) absorption line observations, made in the southern sky with the single dish 15m ESO-SEST telescope, and in the northern sky with the IRAM interferometer. The choice of HCO+ is justified because, due to its large dipole moment, it is generally not excited in diffuse media (the critical density for excitation is $``$ 107 cm-3); therefore confusion with emission is not a problem, contrary to the CO(1-0) line which requires an interferometer to resolve out the emission. Furthermore, the HCO+ absorption survey carried out by Lucas & Liszt (1994, 1996) has revealed more and wider absorption lines than in CO, suggesting that it might be a better tracer. In that study, the derived abundance HCO+/H2 was surprisingly large, of the order of 6$`\times `$10-9, and sometimes even an order of magnitude larger. The details of the observations are presented in Section 2. Section 3 summarizes the results, which are then discussed in Section 4.

## 2  Observations

The observations in the southern sky were carried out with the 15m antenna of ESO-SEST in La Silla (Chile), during 6-10 November 1999. We used two SIS receivers at 3 mm and 2 mm simultaneously, to observe the HCO+(1-0) and CS(3-2) lines at 89.188523 and 146.969033 GHz respectively. Although CS is less abundant, it would have been interesting to have both molecules in case of detection. The HPBW were 57” and 34” and the main-beam efficiencies were $`\eta _{\mathrm{mb}}=T_\mathrm{A}^{}/T_{\mathrm{mb}}`$=0.75 and 0.66 respectively at the two mentioned frequencies. The backends were accousto-optic spectrometers (AOS) both at high-resolution (HRS) and low-resolution (LRS). The corresponding channel spacings (velocity resolutions) were 0.144 (0.268) and 0.087 (0.163) km s-1 at HCO+ and CS for HRS and 2.32 (4.7) and 1.4 (2.8) km s-1 respectively for LRS. The number of channels were 1000 and 1440 for high and low resolution backends respectively, so that the velocity coverage was 140 and 3352 km s-1 at high and low resolution for the HCO+ line, and 85 and 2057 km s-1 for CS respectively. Since all backends were centered of the expected HVC velocity, there was no problem detecting any galactic line around V=0 km s-1 with the low-resolution, but it was most of the time outside of the range at high-resolution. We have retrieved the HCO+ absorptions already reported by Lucas & Liszt (1996) with the IRAM interferometer. In cases where dilution in large velocity channels made detection problematic, we shifted the high-resolution backend to zero velocity to verify the detection. Pointing was corrected regularly (every 2 hours) using known SiO masers (and the 3 mm receiver retuned accordingly). The weather was clear throughout the run, and the typical system temperatures were 180 K for both the 3 and 2 mm ranges. The observing procedure was dual beam switching at high frequency (6 Hz) between same elevation positions in the sky (beam throw of 2’ 27”), to eliminate atmospheric variations. Each source was observed on average for 2 hours, reaching about 3.5 mK of rms noise in channels of 1.4 MHz (4.7 km s-1 at HCO+).

Because the width of the absorption lines may be expected to be small (even though the HCO+ absorption lines are the wider mm lines, and therefore more favorable for detection), a concern should be noted that line profiles may be diluted in the low resolution spectrograph. The technique proved to be valuable, allowing us to retrieve the HCO+(1-0) absorptions already detected by LL96 for galactic clouds, near zero velocity (see below). We also wished to check that the HCO+(1-0) absorption was not hampered by emission. In one of the sources (2251+158) we observed an offset position (with a beam throw of 12’ for the beam-switch) to check for emission. Emission was not detected at the same signal-to-noise at which the absorption was clearly present.

The observations in the northern sky were carried out with the IRAM interferometer in Plateau de Bure (France), during July, October and November 1999. The interferometer data were made with the standard D configuration (see Guilloteau et al. 1992). The array comprised 4 15–m telescopes. The receivers were 3–mm SIS, giving a typical system temperature of 150–200 K. One of the source, 3C 454.3, was used itself as a phase reference, while bandpass and amplitude calibrations were done using also sources such as 3C 273, MWC 349, 1823+568, 2145+067. The data reduction was made with the standard CLIC software. The synthesized beams are of the order of 6$`\times `$8 arcsec. The auto-correlator was used in three overlapping configurations of bandwidth 160, 80 and 40 MHz and a respective resolution of 2.5, 0.625 and 0.156 MHz, giving a maximum velocity resolution of 0.5 km s-1. The largest bandwidth observed is 540 km s-1.

## 3 Results

Our sources were selected from the strong millimeter quasars that were seen in projection over one of the 17 HVC complexes identified, in the Wakker & van Woerden (1991) recapitulating map. Table 1 displays the characteristics of the sources observed, the name and expected velocity of the HVCs along each line of sight, following the notation of the HVC catalogue of Wakker and van Woerden (1991), as well as the measured continuum flux in Jy at 3 and 2 mm, for all 24 sources observed at SEST at the date of observation (6–10 November 1999). The 4 sources observed with the IRAM interferometer (also in Table 1), have been selected to have MgII detected in absorption by Savage et al. (1993), at very high velocities. The HI in emission at these high velocities was measured by the NRAO-43m HI survey towards 143 quasars of Lockman & Savage (1995). The detection of MgII insures the presence of a minimum metallicity towards these lines of sight (larger than 0.32 solar, in 3C 454.3 for instance), favorable for the detection of HCO+. The positions of the observed sources are plotted in Figure 1 vis-a-vis an HI map of HVCs in Aitoff projection. Note that one source has been observed both with IRAM and SEST (3C 454.3).

The spectra were then normalized to the continuum flux, and the upper limit at 3$`\sigma `$ of the optical depth $`\tau `$ in absorption was computed in each case assuming that the surface filling factor is $`f`$=1, i.e., that the absorbing molecular material covers completely the extent of the mm continuum source, in projection. If $`T_{cont}`$ is the observed continuum antenna temperature of the background source, and $`T_{abs}`$ the amplitude in temperature of the absorption signal, then the optical depth is:

$$\tau =ln(1\frac{T_{abs}}{fT_{cont}})$$

The 3$`\sigma `$ upper limits of $`\frac{T_{abs}}{T_{cont}}`$ as measured in 0.56 km s-1 channels is listed in Table 2.

The total column density of HCO+, observed in absorption between the levels $`u`$ $`<`$$`l`$ with an optical depth $`\tau `$ at the center of an observed line of width $`\mathrm{\Delta }v`$ at half-power, is:

$$N_{\text{HCO}\text{+}}=\frac{8\pi }{c^3}f(T_x)\frac{\nu ^3\tau 𝑑v}{g_uA_u},$$

where $`\nu `$ is the frequency of the transition, $`g_u`$ the statistical weight of the upper level (= 2 Ju+1), $`A_u`$ the Einstein coefficient of the transition (here $`A_u`$ = 3$`\times `$10-5 s-1), $`T_x`$ the excitation temperature, and

$$f(T_x)=\frac{Q(T_x)exp(E_l/kT_x)}{1exp(h\nu /kT_x)}$$

where $`Q(T_x)`$ is the partition function. We assumed statistical equilibrium an excitation temperature, close to the cosmic background temperature, i.e. $`T_x`$ = 3 K, because of the large critical density needed to excite HCO+. We also expect a very narrow linewidth, comparable to the detected lines, and adopted $`dv`$ = 1.1 km s-1 to derive the upper limits in Table 2. The HCO+/H2 abundance was conservatively taken as 6$`\times `$10-9, but it must be kept in mind that it could be more than an order of magnitude higher (e.g. Lucas & Liszt 1994, Wiklind & Combes 1997), and therefore the derived H2 column densities could be correspondingly lower. However, if the metallicity is lower than solar, the corrections should go in the reverse sense.

An indicative HI column density of the high-velocity gas was also estimated using the HI surveys of Stark et al (1992) and Hartmann & Burton (1997) for the northern hemisphere, and Bajaja et al. (1985) for our 5 southernmost sources. This column density is rather uncertain since it has been smoothed over large areas (at least one half of a degree) while the material that could appear in absorption extends over milli-arcseconds, similar to the background millimeter sources. At small scales the HI column density could be much higher than the values presented.

Figure 2 shows some of the low velocity detections. All of them have already been discovered by Lucas & Liszt (1996), except the one at 1923+210 which is new. In the low-resolution backends, though, they are barely resolved and have somewhat reduced peak intensity. To check this, we have re-tuned to their central velocity, and centered the high-resolution spectrograph at V$``$ 0. In the HRS AOS, the absorptions had indeed stronger intensities and were in all cases compatible with previously reported values (the integration time though, for the retuned spectra, was not enough to obtain a high S/N).

Towards the source 1923+210, a tentative detection at the expected HVC velocity was obtained, as shown in Figure 3. It is very narrow, and was detected clearly only in the HRS back-end.

Akeson and Blitz (1999) have recently reported upper limits in CO absorption with the BIMA and OVRO interferometers towards 7 continuum sources. We have no sources in common, and therefore we increase the statistical significance of the upper limits. They also searched for HI absorption in HVCs with the VLA, and have positive results only in the gas associated to the outer arm of our Galaxy. They conclude that true HVCs are very weak HI and molecular absorbers. HI absorption in HVCs has been searched with single dish or interferometer several times, without much success (Payne et al. 1980, Colgan et al. 1990, Wakker et al. 1991). The fact that only $``$ 5% of the lines of sight towards HVCs show HI absorptions, while this frequency reaches 100% for normal galactic gas (Dickey et al. 1983), sheds some light on the physical structure of the clouds.

## 4 Discussion and Conclusion

### 4.1  The diverse nature of HVCs

It is still difficult to tackle the problem of the origin of HVCs, since they may be diverse in nature, with possibly different formation histories. The first idea that they are clouds infalling towards the Milky Way (Oort, 1966) was proposed since only negative velocities clouds were discovered at this epoch. However, since differential galactic rotation makes an important contribution to those velocities and the tangential velocity of the HVCs is also unknown, it is difficult to ascertain their true three dimensional motion. Now that almost an equal number of clouds are detected with positive high velocities, and that is also true in the various reference frames (e.g. Wakker 1991), it is believed there must be other explanations for at least some of them. Some HVC complexes have been proven to be associated with the Galaxy, in being very close (less than 10 kpc) due to absorption detected in front of Galactic halo stars (e.g. Danly et al. 1993, van Woerden et al. 1999). This supported a Galactic origin for some of the HVCs and more specifically the Galactic fountain model, where gas is ejected in the halo by the star formation feedback mechanisms. The main problems with this scenario are the low metallicity observed in most lines of sight (even though it could explain why clouds have nearly solar metallicity, e.g. Richter et al 1999), and the extreme velocities sometimes reached (up to -450 km s-1 in the negative side). Alternatively, HVCs could be transient structures, now becoming bound to the Galaxy: an ensemble or complex of HVCs has been identified as tidal debris from the Magellanic Clouds (Mathewson et al. 1974), and is called the Magellanic Stream. Few of them could come from tidal debris from interactions with other dwarf galaxies but the corresponding dwarf galaxies either have not been identified yet, or they have been already dispersed (e.g. Mirabel & Cohen 1979).

A key point is to consider whether HVCs are transient structures or coherent and self-gravitating. With only their column density observed in HI, to be self-gravitating they should be at least at 1 Mpc distance, and in average at 10 Mpc, therefore outside the Local Group (Oort, 1966). This distance can be reduced by a factor 10, if the total mass of HVC is taken to be 10 times their HI mass, composed mostly of dark matter (Blitz et al. 1999). Since the specific kinetic energy is in M/R $``$ Distance, then the clouds would have to be only at about 1 Mpc, and would consequently be part of the Local Group. The main difficulty with this model of mini-haloes merging with our Galaxy, is that other high-velocity clouds should have been observed around or in between external galaxies, which is not the case (Giovanelli 1981, Zwaan et al. 1997, Banks et al. 1999). Moreover, the derived typical dimensions and mass of these systems do not correspond to any observed object or any extrapolation of mass ranges (they have dwarf masses, but are very extended in size).

Another possibility, however, could be that HVCs represent gas left over from the formation of the Galaxy: they form a system out of equilibrium, but bound to the Galaxy, and are now raining down to the Galactic disk. This would explain several observed characteristics, such as the 4-10 kpc distance determined for some complexes, and the low metallicity of many of them (e.g. Wakker et al. 1999).

### 4.2  How many molecular absorptions could be expected?

Given the low HI column densities reported in Table 2, it could seem hopeless to detect molecular absorption, with the present sensitivities. But this is true only if the HVC gas is homogeneous. In fact, from previous HI observations, we expect that like the gas in the galactic disk,the HVC gas is also composed of several components, with clumps of much higher column densities, only detectable at higher spatial resolution. This information can be deduced from existing HI observations in emission and absorption, towards HVCs. The optical thickness $`\tau `$ is related to the column density N(HI) (cm-2), the spin temperature Ts(K) and the FWHM velocity width $`\mathrm{\Delta }V`$ (km s-1) by

$$\tau =\frac{N(HI)}{1.8\times 10^{20}}\left(\frac{50}{T_s}\right)\left(\frac{20}{\mathrm{\Delta }V}\right)$$

Since the profile extends at least over 20 km s-1 in emission, and the spin temperature has been determined to be at least 50 K, if there was only one component, the derived optical depth would have to be very low, $`\tau <0.1`$. Absorption and emission studies in the Galactic plane have shown though that there is indeed more than one component. If there was only one, both emission and absorption profiles would look similar, which is not what is observed. In fact, there are at least two components; a warm diffuse inter-clump component with cloudlets which are cold, narrow in velocity, and more optically thick (Garwood & Dickey 1989). If the surface filling factor of the two components are f1 and f2, for spin temperatures T1 and T2, and optical depths $`\tau _1`$ and $`\tau _2`$, the observed ratio between the absorption depth $`\frac{T_{abs}}{T_{cont}}`$ and the antenna temperature of the emission $`T_{em}`$ is

$$\frac{T_{abs}}{T_{cont}T_{em}}=\frac{f_1(1e^{\tau _1})+f_2(1e^{\tau _2})}{T_1f_1(1e^{\tau _1})+T_2f_2(1e^{\tau _2})}$$

In this formula, it is obvious that each component is weighted according to its mass if it is optically thin (i.e. weight $`f\tau `$), but considerably less if $`\tau >>1`$. Therefore, if the cold component is optically thick, the derived spin temperature will be overestimated111In fact the mass of the cold component would be itself under-estimated, since the absorption often saturates, while the emission, dominated by the warm gas, saturates less.

Are HVC clouds of the same nature than normal low-velocity galactic clouds, and have they similar small-scale structure? For normal HI clouds, Payne et al. (1983) have determined (from absorption/emission comparisons) that the weighted average spin temperature is decreasing as the optical depth increases (cf line in Figure 4). There is only a small scatter in this relation, which means that if the cold and thick component is made of cloudlets, their size must be smaller than that of their background continuum sources, i.e. a fraction of an arcmin, and their number must be large accordingly (N $`>`$ 100). We do not see the situation where absorption features are deep and rare (statistically the Ts-$`\tau `$ relation will still hold, but with large scatter). The data favor a model, in which the cloudlets are quite small ($`<`$ 0.1 pc) and numerous, and they are weighted according to their surface filling factor $`f`$ both in emission and in absorption for any line of sight. The existence of such small scale structure is also confirmed by VLBI HI absorption (Faison et al. 1998), where sizes down to $``$ 20 AU are detected. It is also very likely that the structure, apart from these smallest fragments, has no particular scale. If it is a fractal, statistically, there is a correlation between the optical depth between scales with a limited scatter. This would explain the observed correlation between emission and absorption at different scales. When the emission/absorption measurements for HVCs are considered (cf Figure 4) the lower limits on derived spin temperature are compatible with the detections on the normal low-velocity gas and their Ts-$`\tau `$ relation. The spin temperature of HVCs is a weighted mean of the warm and cold components, with the same mixtures as the one observed in normal low-velocity clouds of the galactic plane. The difficulty to find HI in absorption in HVCs corresponds then only to their low average column density, and not to a different physical structure.

As for molecular absorptions, the column densities to which a detection is possible is even larger. The corresponding scales must be smaller, and consequently the corresponding line-widths narrower. This is observed for low-velocity absorptions, where the detected line-widths are as narrow as 0.6 km s-1(LL96). The detected optical depths are larger on average, and the probability to underestimate the column density is higher, because of saturation. (One should note though that the apparent optical depth is low because of spatial and velocity dilutions.) The probability of detection of the HCO+(1-0) absorption has been estimated to be 30% as large as the 21cm absorption for galactic clouds (LL96). The presently observed low probability to find an HCO+(1-0) absorption is therefore expected. In addition, there could be a column density threshold for self-shielding against photo-dissociation, that hampers molecular observations. This threshold has been estimated for CO emission to N(H2) $``$ 4$`\times `$1020 cm-2 (or equivalently of the order of 1012 cm-2 for HCO+). If our tentative detection is confirmed, given the low metallicity of the HVCs, this will support the existence of clumps of high column densities in this medium. The fact that molecular absorption is more frequent with respect to emission than atomic absorption is related to the excitation mechanism. Large volumic critical densities are required to excite molecules above the cosmic background, and this is in particularly true for HCO+. This makes absorption techniques the more promising to probe the molecular content of HVCs in the future.

### 4.3  Physical nature and distance of the gas

Since the HVCs appear to follow in projection the same fractal properties as the normal low-velocity gas (Vogelaar & Wakker 1994), it could be interesting to develop an insight in their distance from their size-linewidth relation. It is now well established that clouds in the interstellar medium (either molecular or atomic) are distributed according to a self-similar hierarchical structure, characteristic of a fractal structure (Falgarone et al. 1991; Stanimirovic et al. 1999; Westpfahl et al. 1999). Such a scaling relation between mass and size, can also lead to a relation between size and line-width, provided that the structures are virialized. In particular, various clouds at all scales obey a power-law relation between sizes $`R`$ and line-widths or velocity dispersion $`\sigma `$:

$$\sigma R^q$$

with $`q`$ between 0.35 and 0.5 (e.g. Larson 1981, Scalo 1985, Solomon et al 1987). We have plotted this latter relation, together with the sizes and line-widths of the 65 well defined isolated HVCs, catalogued by Braun & Burton (1999). This catalog is expected to be free from galactic contamination as well as from blending along the line of sight, because of the isolation criterium imposed for their selection. To compute their sizes, two distances were assumed, either 20 kpc, or 1 Mpc, and the geometrical mean between major and minor axis was calculated. At a distance of 20 kpc, the clouds fall on the relation corresponding to Giant Clouds in the Galaxy. Note that the large scatter is due to the fact that this choice of distance is only one order of magnitude, and the HVCs are certainly not all at the same distance. This set of clouds has been determined with a spatial resolution of half a degree. The clouds determined at higher spatial resolution have correspondingly narrower line-widths. In Figure 5, we have also plotted the characteristics of clouds determined with the Westerbork interferometer, at 1 arcmin resolution (Wakker & Schwarz 1991). They also fit the galactic clouds relation on average, if their distance is chosen to be 20 kpc, with large scatter since individual distances are also not known. In fact, HI observations at different spatial resolutions emphasize a particular scale of the hierarchical structure (see e.g the 10’ resolution observations by Giovanelli & Haynes 1977). This hierarchical structure is similar to what is observed for “normal” galactic clouds, in the sense that the same fraction 20-30% of the single dish flux is retrieved in the interferometer data (Wakker & Schwarz 1991).

The size-linewidth relation has been widely observed up to 100pc in size, the largest size for self-gravitating clouds in the Galaxy, but it might appear questionable to extend it to higher scales, where the gas would not be self-gravitating. At these scales, the gas is bound into largest self-gravitating structures, including stars or dark matter. However, even at these scales, the gas should trace the gravitational potential of the bound structure it is embedded in, and share the corresponding velocity dispersion; such a relation is observed for instance in the form of the Tully-Fisher relation in galaxies. The main point is that the gas should reveal velocity profiles in emission that should grow wider with the distance, if it belongs to an assumed self-gravitating remote system. The observed profile width is therefore a distance indicator.

### 4.4 Conclusion

We have searched for HCO+(1-0) absorption towards 27 high velocity clouds, in front of remote radio-loud quasars. The technique is efficient, since we detect the existing absorption due to low velocity galactic clouds, for our low latitude sources. Only one tentative HVC detection is reported. If confirmed, this indicates the presence of small scale cloudlets, at low excitation and high column densities, prolonging the hierarchical structure already observed in the atomic component at larger scale. When this hierarchical structure is compared to the one observed for low-velocity galactic clouds, a good fit is obtained for the self-similar relation between sizes and line-widths, if the HVCs are on average at 20 kpc distance. Since mm molecular absorptions are expected to be more frequent than emission for these low column density HVCs, this absorption technique appears promising to probe the molecular component of HVCs, already directly detected by UV H2 absorption lines (Richter et al 1999).

###### Acknowledgements.

We are very grateful to R. Giovanelli for useful comments on the manuscript, to B. Wakker and F. Mirabel for stimulating discussions, and an anonymous referee for constructive criticism. We also thank the SEST staff for their kind help during the observations, and Raphael Moreno and Robert Lucas for their assistance in the IRAM interferometer data reduction.


text:
# The model of the ideal crystal as a criterion for evaluating of the approximate equations of the liquids.

## Introduction

The structure and thermodynamics of both dense gases and liquids is described by a pair correlation function $`h_{12}`$ considering the collective effects in dense mediums. Nowadays about 20 approximate integral equations of the Ornstein-Zernike (OZ) type connecting the direct $`C_{12}`$ and pair $`h_{12}`$ correlation functions are proposed for describing of the above-mentioned one . The degree of exactness of every such approximation is impossible to be evaluated. The physical meaning of their basic approximations has not been cleared up to the end yet. Thus such a situation suggests a choice of maximum exact approximations in a comparison with the result achieved at the numerical experiment. Nevertheless such a comparison doesn’t reveal the physical meaning of approximations.

The OZ equation is to be used for the spatial homogenous and isotropic mediums as in such a case a two-particle distribution function (as well as a pair correlation function) depends only on a mutual distance between the particle centers $`r_{12}`$, that makes all the calculations much more simplified.

But there exists a more generalized form of the OZ equation for the spatial inhomogenious anisotropic mediums . It has not been used widely yet for the solution of more exact problems. One can mention its use only for the description of the liquid-solid phase transition . This work describes the use of the Martynov-Sarkisov approximation, which gives the best agreement with the data of the numerical experiment for the hard spheres system .

In this work we suggest using the generalized OZ equation for the description of the ideal crystal at $`T=0`$. The pair correlation function $`h_{12}`$ in this limit case takes the meaning of the Dirak $`\delta `$ function. As a result, a linear integral equation for the direct correlation function is achieved, which has a simple analytical solution. It should fit The results known from crystallophysics for the ideal crystal. So the limit transition to the model of the ideal crystal may be considered as a physical criterion for the evaluation of the exactness for the approximations used in physics of liquids.

## 1 Initial equations

In works  it was shown that a hierarchy of Bogolubov- Born-Green-Kirkwood-Yvon (BBGKY) equations may be modified into a two equations system

$$\omega _1=nG_2S_{12}d(2)+\mathrm{ln}a$$
(1)
$$h_{12}=C_{12}+nG_3C_{13}h_{23}d(3)$$
(2)
for two unknown functions: a one-particle distribution function $`G_1(\stackrel{}{r}_1)=\mathrm{exp}(\omega _1(\stackrel{}{r}_1))`$ and a two-particle distribution function

$$G_{ij}(\stackrel{}{r}_i,\stackrel{}{r}_j)=G_iG_j(1+h_{ij}),$$
(3)
$$h_{ij}=1+\mathrm{exp}(\frac{\mathrm{\Phi }_{ij}}{\mathrm{\Theta }}+\mathrm{\Omega }_{ij}(\stackrel{}{r}_i,\stackrel{}{r}_j)),$$
(4)
where $`n=N/V`$ is density, $`\mathrm{\Phi }_{ij}`$-molecular interaction potential, $`\mathrm{\Theta }=kT`$-temperature, $`d(i)=d\stackrel{}{r}_i`$\- a volume integral element of the i particle.

All previous distribution functions are expressed through $`G_1`$ and $`G_{12}`$. The direct correlation functions $`S_{ij}`$, $`C_{ij}`$ in equations (1) and (2) are evidently expressed through infinite integral sets distinguished from the products of the pair correlation functions $`h_{ij}`$

$$S_{ij}=h_{ij}\mathrm{\Omega }ij\frac{1}{2}h_{ij}(\mathrm{\Omega }_{ij}+\frac{1}{6}M_{ij}^{(1)}),$$
(5)
$$C_{ij}=h_{ij}\mathrm{\Omega }_{ij}+\frac{1}{2}M_{ij}^{(2)},$$
(6)
in which

$$M_{ij}^{(k)}=n^2G_3G_4h_{i3}h_{i4}h_{34}h_{3j}h_{4j}d(3)d(4)+\mathrm{},k=1,2$$
(7)
the so-called bridge-functionals represent infinite sums of non-reduced diagrams.

For spatial homogeneous and isotropic systems (dense gases and liquids) at $`\omega _1=0,G_1=1,G_{12}=G_{12}(\stackrel{}{r}_{12})`$, equation (1) is a definition of the activity factor logarithm $`\mathrm{ln}a`$. Equation (2) describing the neighboring order in liquids tends to come to a well-known OZ ratio

$$h_{12}=C_{12}+nC_{13}h_{13}d(3),$$
(8)
being the basis of the modern theory of liquids and molds . For making ratio (8) closed it is necessary to set an approximation connecting the direct correlation function $`C_{12}(\stackrel{}{r}_{12})`$ with the pair correlation function $`h_{12}(\stackrel{}{r}_{12})`$.

## 2 The ideal crystal

One particle distribution function has the meaning of local density in laboratory coordinate system. For spatially homogeneous isotropic mediums one particle distribution function equals one because the external field does not exist. For the crystal condition one particle distribution function does not equal one, even if the external field does not exist. To describe such a system it is necessary to introduce the external field according to Bogolubov which fixes the crystal place in the space and then to make it tend to zero. Then one particle distribution function describes the local density distribution in the regard to the fixed coordinate system giving the crystal place as a whole. As an origin of such a coordinate system it is convenient to choose one of lattice particles giving it number zero conditionally. Therefore one particle distribution function $`G_1=\mathrm{exp}(\omega _1)`$ for the crystal can be represented in the form of the periodic function

$$G_1(\stackrel{}{r}_1)=\mathrm{`}\underset{\stackrel{}{k}}{}G_\stackrel{}{k}\mathrm{exp}(ı\stackrel{}{k}\stackrel{}{r}_1),$$
(9)
For the ideal crystal at $`T=0`$ every Fourier’s component $`G_\stackrel{}{k}`$ is similar and $`G_1`$ is a superposition of three-dimension Dirak $`\delta `$ functions

$$G_1(\stackrel{}{r}_1)=\underset{\stackrel{}{r}_n}{}\delta (\stackrel{}{r}_1\stackrel{}{r}_n)$$
(10)
where the summation is done by crystal lattice nodes $`\stackrel{}{r}_n`$.whose coordinates, in their turn, must be defined.

The mutual arrangement of lattice nodes (that is the lattice period and the type of the crystal system) is defined by the potential of molecular interaction. On the other hand, the potential $`\mathrm{\Phi }_{12}`$ enters the pair correlation function in the form of the combination $`\frac{\mathrm{\Phi }_{12}}{\mathrm{\Theta }}`$. Let us consider the kind of the function $`h_{12}`$ at $`T=0`$. Let the molecular interaction be described by Lenard-Jones potential

$$\mathrm{\Phi }_{12}=4\epsilon [(\frac{\sigma }{r})^{12}(\frac{\sigma }{r})^6],$$
(11)
where $`\sigma `$ is a characteristic size of a molecule. The potential $`\mathrm{\Phi }_{12}`$ has a minimum at the point $`r_0=\sigma \sqrt[6]{2}`$. Therefor the function $`\frac{\mathrm{\Phi }_{12}}{\mathrm{\Theta }}`$ at $`T0`$ has $`\delta `$ -shaped maximum at this point. That is why one can neglect the thermal potential $`\omega _{12}`$ describing the neighbouring order. As a result $`h_{12}`$ is approximated one-dimension Dirak function $`\delta (r_{12}r_0)`$.

As a result at $`T=0`$ we get the following equation for the straight correlation line with regard to (10)

$$C_{12}^{(2)}+n\underset{\stackrel{}{r}_n}{}C_{12}^{(2)}(\stackrel{}{r}_1,\stackrel{}{r}_n)\delta (r_{2n}r_0)=\delta (r_{12}r_0).$$
(12)
We notice that (12) is the linear equation whose solution is sought in the form

$$C_{12}=\alpha \delta (r_{12}r_0),$$
(13)
where $`\alpha `$ is a coefficient to be defined. Substitution $`C_{12}`$ in (12) results in the following expression

$$\delta (r_{12}r_0)=\alpha \delta (r_{12}r_0)+n\alpha \underset{\stackrel{}{r}_n}{}\delta (\stackrel{}{r}_1\stackrel{}{r}_nr_0)\delta (\stackrel{}{r}_2\stackrel{}{r}_nr_0).$$
(14)
Particles 1 and 2 are the neighbouring ones. The summation is done by those nodes which are the nearest both for the first particle and for the second one. Let such particles have $`N_0`$ numbers. Using (14) we get

$$\alpha =\frac{1}{1+nN_0},r_{12}=r_0,r_{13}=r_0,r_{23}=r_0$$
(15)
The correlation (15) defines the crystal structure (the lattice period and the type of the crystal system). For determining the crystal system we should calculate the number $`N_0`$.

At $`T=0`$ the system is densely packed. There are two types of lattices with the dense packing - face centered cubic and hexagonal lattices . Their structure is formed by successive layers of densety packed planes. Every particle has twelve neighbouring particles. This structure type is connected with the distant order in the crystal. But in any substance (including the crystal) there is the neighbouring order which is described by the second addend in the right-hand side (14) in this case.

Let us take arbitrarily a couple of the neighbourong particles arranged in the plane $`(111)`$. It has four particles juxtaposed with it for both types of the lattice: two particles in the plane (111) and one particle in every adjoined plane. If particles 1 and 2 lie in two neighbouring planes the situation is different. For the face centered cubic lattice $`N_0`$ is 4 as before but for the hexagonal lattice $`N0`$ is 3. So $`N_0=`$const for the face centered cubic lattice. As the pair of the neighbouring particles is chosen arbitrarily this indicates that the face centered cubic lattice is realized. It corresponds to the experimental data for crystals of inert gases. However for Lenard-Jones potential the hexagonal structure has much lower energy than the face centered cubic lattice therefor it is this lattice that must be realized. The problem of the crystal system is not solved in this paper yet.

Now we show that solutions (10) and (13) satisfy the equation (1). The direct correlation function $`C_{12}^{(1)}`$ neglecting two particle correlations $`\omega _{12}`$ equals

$$C_{12}^{(1)}=C_{12}^{(2)}=\alpha \delta (r_{12}r_0).$$
(16)
Substitution this expression in (1) we shall get

$$\omega _1=n\alpha \underset{\stackrel{}{r}_n}{}\delta (\stackrel{}{r}_1\stackrel{}{r}_nr_0)+\mathrm{ln}a.$$
(17)
Let $`a=1`$ and doing summation by $`\stackrel{}{r}_{12}`$ as it is done in (14)

$$\omega _1=n\alpha N_0\delta (\stackrel{}{r}_1\stackrel{}{R}_0r_0)+\mathrm{ln}a.$$
(18)
where $`\stackrel{}{R}_0`$ is a radius of the vector-particle placed in the coordinate system origin. Since coordinates of all the nodes are known now, $`\omega _1`$ is a given function $`G_1`$ can be given in the form (10).

The complicity of problems being solved by the physics of condensed matter makes one use different physically based approximations. In particular, in the physics of plasma and solids an approximation of the self-coordinated field is widely used.

In the physics of liquids a superpositional approximation is well-known, which is used to express a triple function of the distribution through two-particle ones. It is to the superpositional approximation, that fits to the hypernetted chain equation, which results from (2) by the neglect of all the irreducible diagrams. Summing up of such diagrams is practically unrealizable. Physically it is connected with the fact that at the limit temperatures it is necessary to take into account the collective effects, stimulated by a molecular motion. That is why it is necessary to offer a physical value criterion of the irreducible diagrams.

A limit transition to the ideal crystal at $`T=0`$ represent such a criterion. In this case it is possible to neglect the collective effects connected with the molecular motion. As a result a limit ratio for the direct correlation function $`C_{12}`$, that effectively includes a contribution of the irreducible diagrams, is possible to be obtained.

From a great number approximations between $`C_{12}`$ and $`h_{12}`$ the most physically valid is that one which fits to the given limit ratio.

## Conclusion

The solution of Ornstein-Zernike generalized equation is obtained for the ideal crystal at $`T=0`$. In this case the pair correlation function $`h_{12}`$ Degenerates to Dirak $`\delta `$ function and for the direct correlation function $`C_{12}`$ the linear integral equation is found which has the analytical solution. By using it the main problem of physics of liquids is solved - establishment of closure between the direct and pair correlation functions.

At the same time there is still a problem for the aggregate condition, the method developed by us can be used as a criterion for evaluating the closures: those resulting in the solution for the ideal crystal at $`T=0`$ will have the physical meaning.


text:
# First-principles calculations of hot-electron lifetimes in metals

## I Introduction

Low-energy excited electrons in metals, with energies larger than $`0.5\mathrm{eV}`$ above the Fermi energy, experience strong electron-electron (e-e) scattering processes. Although inelastic lifetimes of these so-called hot electrons have been investigated for many years on the basis of the free-electron-gas (FEG) model of the solid, time-resolved two-photon photoemission (TR-2PPE) experiments have shown the key role that band-structure effects may play in the decay mechanism. First-principles calculations of hot-electron lifetimes that fully include the band structure of the solid have been reported only very recently for aluminum and copper. These calculations show that actual lifetimes are the result of a delicate balance between localization, density of states, screening, and Fermi-surface topology, even in the case of a free-electron-like metal such as aluminum.

In this paper, we report first-principles calculations of inelastic lifetimes of excited electrons in a variety of real metals. We start with free-electron-like trivalent (Al) and divalent (Mg) metals, and then focus on divalent Be and the role that $`d`$ electrons play in a noble metal like Cu. First, we expand the one-electron Bloch states in a plane-wave basis, and solve the Kohn-Sham equation of density-functional theory (DFT) by invoking the local-density approximation (LDA) for exchange and correlation (XC). The electron-ion interaction is described by means of non-local, norm-conserving ionic pseudopotentials, and we use the one-electron Bloch states to evaluate the screened Coulomb interaction in the random-phase approximation (RPA). We finally evaluate the lifetime of an excited Bloch state from the knowledge of the imaginary part of the electron self-energy, which we compute within the GW approximation of many-body theory. Our calculations indicate that scattering rates may strongly depend, for a given electron energy, on the direction of the wave vector of the initial state. Also, average lifetimes, as obtained by averaging over all wave vectors and bands with the same energy, are found to deviate considerably from those derived for a FEG.

The rest of this paper is organized as follows: Explicit expressions for the electron decay rate in periodic crystals are derived in section II, within the GW approximation of many-body theory. Calculated inelastic lifetimes of hot electrons in Al, Mg, Be, and Cu are presented in section III, and the conclusions are given in section IV. Atomic units are used throughout, i.e., $`e^2=\mathrm{}=m_e=1`$.

## II Theory

Take an inhomogeneous electron system. In the framework of many-body theory, the damping rate $`\tau _i^1`$ of an excited electron in the state $`\varphi _i(𝐫)`$ with energy $`E_i`$ is obtained from the knowledge of the imaginary part of the electron self-energy, $`\mathrm{\Sigma }(𝐫,𝐫^{};E_i)`$, as

$$\tau _i^1=2d𝐫d𝐫^{}\varphi _i^{}(𝐫)\mathrm{Im}\mathrm{\Sigma }(𝐫,𝐫^{};E_i)\varphi _i(𝐫^{}).$$
(1)
In the GW approximation, one considers only the first-order term in a series expansion of the self-energy in terms of the screened Coulomb interaction:

$$\mathrm{\Sigma }(𝐫,𝐫^{};E_i)=\frac{i}{2\pi }𝑑EG(𝐫,𝐫^{};E_iE)W(𝐫,𝐫^{};E),$$
(2)
where $`G(𝐫,𝐫^{};E_iE)`$ represents the one-particle Green function and $`W(𝐫,𝐫^{};E)`$ is the time-ordered screened Coulomb interaction. After replacing the Green function ($`G`$) by the zero order approximation ($`G^0`$), the imaginary part of the self-energy can be evaluated explicitly:

$$\mathrm{Im}\mathrm{\Sigma }(𝐫,𝐫^{};E_i)=\underset{f}{}\varphi _f^{}(𝐫^{})\mathrm{Im}W(𝐫,𝐫^{};\omega )\varphi _f(𝐫),$$
(3)
where $`\omega =E_iE_f`$ represents the energy transfer, the sum is extended over a complete set of final states $`\varphi _f(𝐫)`$ with energy $`E_f`$ ($`E_FE_fE_i`$), $`E_F`$ is the Fermi energy, and

$`W(𝐫,𝐫^{};\omega )=`$ $`v(𝐫𝐫^{})+{\displaystyle d𝐫_1d𝐫_2v(𝐫𝐫_1)}`$ (6)
$`\times \chi (𝐫_1,𝐫_2;\omega )v(𝐫_2𝐫^{}).`$
Here, $`v(𝐫𝐫^{})`$ represents the bare Coulomb interaction, and $`\chi (𝐫,𝐫^{};\omega )`$ is the density-density correlation function of the solid.

In the framework of time-dependent density-functional theory (TDDFT), the density-density correlation function satisfies the integral equation

$`\chi (𝐫,𝐫^{};\omega )`$ $`=\chi ^0(𝐫,𝐫^{};\omega )+{\displaystyle d𝐫_1d𝐫_2\chi ^0(𝐫,𝐫_1;\omega )}`$ (9)
$`\times [v(𝐫_1𝐫_2)+K^{xc}(𝐫_1,𝐫_2;\omega )]\chi (𝐫_2,𝐫^{};\omega ),`$
where $`\chi ^0(𝐫,𝐫^{};\omega )`$ is the density-density correlation function of noninteracting Kohn-Sham electrons, as described by the solutions of the time-dependent counterpart of the Kohn-Sham equation. In usual practice, these amplitudes are approximated by standard LDA wave functions. The kernel $`K^{xc}(𝐫_1,𝐫_2;\omega )`$, which accounts for the reduction in the e-e interaction due to the existence of short-range exchange-correlation (XC) effects, is obtained from the knowledge of the XC energy functional. In the RPA, this kernel is taken to be zero.

For periodic crystals, one may introduce the following Fourier expansion for the screened interaction of Eq. (6):

$`W(𝐫,𝐫^{};\omega )=`$ $`{\displaystyle \frac{1}{\mathrm{\Omega }}}{\displaystyle \underset{𝐪}{\overset{BZ}{}}}{\displaystyle \underset{𝐆,𝐆^{}}{}}\mathrm{e}^{\mathrm{i}(𝐪+𝐆)𝐫}\mathrm{e}^{\mathrm{i}(𝐪+𝐆^{})𝐫^{}}`$ (12)
$`\times v_𝐆(𝐪)ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega ),`$
where the first sum is extended over the first Brillouin zone (BZ), $`𝐆`$ and $`𝐆^{}`$ are reciprocal lattice vectors, $`\mathrm{\Omega }`$ is the normalization volume, $`v_𝐆(𝐪)`$ represent the Fourier coefficients of the bare Coulomb interaction, and $`ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )`$ are the Fourier coefficients of the inverse dielectric function,

$$ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )=\delta _{𝐆,𝐆^{}}+\chi _{𝐆,𝐆^{}}(𝐪,\omega )v_𝐆^{}(𝐪).$$
(13)
Within RPA,

$$ϵ_{𝐆,𝐆^{}}(𝐪,\omega )=\delta _{𝐆,𝐆^{}}\chi _{𝐆,𝐆^{}}^0(𝐪,\omega )v_𝐆^{}(𝐪),$$
(14)
where $`\chi _{𝐆,𝐆^{}}^0(𝐪,\omega )`$ are the Fourier coefficients of the density-density correlation function of non-interacting Kohn-Sham electrons (see, e.g., Ref.).

After introduction of the Fourier representation of Eq. (12) into Eq. (3), and in the limit that the volume of the system $`\mathrm{\Omega }`$ becomes infinite, one finds the following expression for the damping rate of an electron in the state $`\varphi _{𝐤,n_i}(𝐫)`$ with energy $`E_{𝐤,n_i}`$:

$`\tau _i^1={\displaystyle \frac{1}{\pi ^2}}{\displaystyle \underset{f}{}}{\displaystyle _{\mathrm{BZ}}}d𝐪{\displaystyle \underset{𝐆,𝐆^{}}{}}`$ $`{\displaystyle \frac{B_{if}^{}(𝐪+𝐆)B_{if}(𝐪+𝐆^{})}{\left|𝐪+𝐆\right|^2}}`$ (17)
$`\times \mathrm{Im}\left[ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )\right],`$
where $`\omega =E_{𝐤,n_i}E_{𝐤𝐪,n_f}`$, and

$$B_{if}(𝐪+𝐆)=d𝐫\varphi _{𝐤,n_i}^{}(𝐫)\mathrm{e}^{\mathrm{i}(𝐪+𝐆)𝐫}\varphi _{𝐤𝐪,n_f}(𝐫).$$
(18)
Couplings of the wave vector $`𝐪+𝐆`$ to wave vectors $`𝐪+𝐆^{}`$ with $`𝐆𝐆^{}`$ appear as a consequence of the existence of electron-density variations in real solids. If these terms, representing the so-called crystalline local-field effects, are neglected, one can write

$$\tau _i^1=\frac{1}{\pi ^2}\underset{f}{}_{\mathrm{BZ}}d𝐪\underset{𝐆}{}\frac{\left|B_{if}(𝐪+𝐆)\right|^2}{\left|𝐪+𝐆\right|^2}\frac{\mathrm{Im}\left[ϵ_{𝐆,𝐆}(𝐪,\omega )\right]}{|ϵ_{𝐆,𝐆}(𝐪,\omega )|^2}.$$
(19)
Within RPA, Eq. (14) yields

$`\mathrm{Im}\left[ϵ_{𝐆,𝐆}(𝐪,\omega )\right]={\displaystyle \frac{2\pi v_𝐆(𝐪)}{\mathrm{\Omega }}}{\displaystyle \underset{𝐤}{\overset{BZ}{}}}{\displaystyle \underset{n,n^{}}{}}(f_{𝐤,n}f_{𝐤+𝐪,n^{}})`$ (20)
(21)
$`\times |\varphi _{𝐤,n}|e^{\mathrm{i}(𝐪+𝐆)𝐫}|\varphi _{𝐤+𝐪,n^{}}|^2\delta (\omega E_{𝐤+𝐪,n^{}}+E_{𝐤,n}).`$ (22)
Hence, the imaginary part of $`ϵ_{𝐆,𝐆}(𝐪,\omega )`$ represents a measure of the number of states available for real transitions involving a given momentum and energy transfer $`𝐪+𝐆`$ and $`\omega `$, respectively, which is renormalized by the coupling between initial and final states. The factor $`\left|ϵ_{𝐆,𝐆}(𝐪,\omega )\right|^2`$ in Eq. (19) accounts for the screening in the interaction with the probe electron. Initial and final states of the probe electron enter through the coefficients $`B_{if}(𝐪+𝐆)`$.

If all one-electron Bloch states entering both the coefficients $`B_{if}(𝐪+𝐆)`$ and the dielectric function $`ϵ_{𝐆,𝐆^{}}(𝐪,\omega )`$ were represented by plane waves, then Eqs. (17) and (19) would exactly coincide with the GW scattering rate of excited electrons in a FEG, as obtained by Quinn and Ferrell and by Ritchie. For hot electrons with energies very near the Fermi level ($`E_iE_F`$) this result yields, in the high-density limit ($`r_s<<1`$), the well-known formula of Quinn and Ferrell,

$$\tau _i^{QF}=263r_s^{5/2}(E_iE_F)^2\mathrm{eV}^2\mathrm{fs}.$$
(23)
For a detailed discussion of the range of validity of this approach, see Ref..

We note that the decay $`\tau _i^1`$ of hot electrons in periodic crystals depends on both the wave vector $`𝐤`$ and the band index $`n_i`$ of the initial Bloch state. Nevertheless, we also define $`\tau ^1(E)`$, as the average of $`\tau ^1(𝐤,n)`$ over all wave vectors and bands lying with the same energy in the irreducible wedge of the Brillouin zone (IBZ). Decay rates of hot electrons lying outside the IBZ are considered by simply using the symmetry property $`\tau ^1(S𝐤,n)=\tau ^1(𝐤,n)`$, where $`S`$ represents an operator of the point group of the crystal.

For the evaluation of the polarizability $`\chi _{𝐆,𝐆^{}}^0(𝐪,\omega )`$ and the coefficients $`B_{if}(𝐪+𝐆)`$, Eq. (18), we use the self-consistent LDA eigenfunctions of the one-electron Kohn-Sham hamiltonian of DFT, which we first expand in a plane wave basis,

$$\varphi _{𝐤,n}(𝐫)=\frac{1}{\mathrm{\Omega }}\underset{𝐆}{}u_{𝐤,n}(𝐆)e^{\mathrm{i}(𝐤+𝐆)𝐫}.$$
(24)
The electron-ion interaction is described by means of non-local, norm-conserving ionic pseudopotentials, and the XC potential is obtained in the LDA with use of the Perdew-Zunger parametrization of the XC energy of Ceperley and Alder.

Well-converged results have been found with the introduction in Eq. (24) of kinetic-energy cutoffs of $`12`$, $`6`$, and $`20\mathrm{Ry}`$ for Al, Mg, and Be, respectively. In the case of Cu, all $`4s^1`$ and $`3d^{10}`$ Bloch states have been kept as valence electrons in the pseudopotential generation, and an energy-cutoff as large as $`75\mathrm{Ry}`$ has been required, thereby keeping $`900`$ plane waves in the expansion of Eq. (24). Though all-electron schemes, such as the full-potential linearized augmented plane-wave (LAPW) method, are expected to be better suited for the description of the response of localized $`d`$ electrons, the plane-wave pseudopotential approach has already been successfully incorporated in the description of the dynamical response of copper.

Samplings over the BZ required for the evaluation of both the dielectric matrix and the hot-electron decay rate have been performed on Monkhorst-Pack (MP) meshes: $`20\times 20\times 20`$ for Al, $`24\times 24\times 10`$ for Mg, $`24\times 24\times 16`$ for Be, and $`16\times 16\times 16`$ for Cu. For hot-electron energies under study ($`EE_F0.54.0\mathrm{eV}`$), the inclusion of up to 40 bands has been required, and the sum in Eq. (19) has been extended over $`15`$ $`𝐆`$ vectors of the reciprocal lattice, the magnitude of the maximum momentum transfer $`𝐪+𝐆`$ being well over the upper limit of $`2q_F`$ ($`q_F`$ is the Fermi momentum). For the evaluation of hot-electron lifetimes from Eq. (17), with full inclusion of crystalline local-field effects, dielectric matrices as large as $`40\times 40`$ have been considered.

## III Results and discussion

### A Aluminum

Due to the free-electron-like nature of the energy bands of face-centered cubic (fcc) aluminum \[see Fig. 1\], a simple metal with no $`d`$ bands, the impact of the band structure on the electronic excitations had been presumed for many years to be small. However, X-ray measurements and careful first-principles calculations of the dynamical density-response of this material have shown that band-structure effects cannot be neglected. Full band-structure calculations of the electronic stopping power of Al for slow ions have shown that the energy loss is $`7\%`$ larger than that of a FEG. Our present calculations indicate that actual hot-electron lifetimes in Al are $`35\%`$ smaller than those of electrons in a FEG.

Our ab initio GW-RPA calculation of the average lifetime $`\tau (E)`$ of hot electrons in Al, as obtained from Eq. (17) with full inclusion of crystalline local-field effects, is presented in Fig. 2 by solid circles. The GW-RPA lifetime of hot electrons in a FEG with the electron density equal to that of valence electrons in Al ($`r_s=2.07`$) is exhibited in the same figure, by a solid line. Our calculations indicate that the lifetime of hot electrons in Al is, within RPA, smaller than that of electrons in a FEG with $`r_s=2.07`$ by a factor of $`0.65`$. We have performed band-structure calculations of Eq. (17) with and without \[see also Eq. (19)\] the inclusion of crystalline local-field corrections, and have found that these corrections are negligible for electron energies under study. This is an expected result, since Al crystal does not present strong density gradients nor special electron density directions (bondings).

In order to understand the origin of band-structure effects on hot-electron lifetimes in Al, we first focus on the role that the band structure plays in the creation of electron-hole (e-h) pairs. Hence, we evaluate hot-electron lifetimes from either Eq. (17) or Eq. (19) by replacing the electron initial and final states in $`|B_{if}(𝐪+𝐆)|^2`$ by plane waves (plane-wave calculation). The result we obtain with full inclusion of the band structure of the crystal in the evaluation of $`\mathrm{Im}ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )`$ is represented in Fig. 2 by open triangles. Due to splitting of the band structure over the Fermi level, new channels are opened for e-h pair production, and band-structure effects tend, therefore, to decrease the lifetime of very-low-energy electrons by $`5\%`$, as in the case of slow ions.

In the case of moving ions, differences between actual decay rates and those obtained in a FEG only enter through the so-called energy-loss matrix, $`\mathrm{Im}[ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )]`$. However, hot-electron decay rates are also sensitive to the actual initial and final states entering the coefficients $`B_{if}(𝐪+𝐆)`$. Differences between our full (solid circles) and plane-wave (open triangles) calculations come from this sensitivity of hot-electron initial and final states on the band structure of the crystal, showing that the splitting of the band structure over the Fermi level now plays a major role in lowering the hot-electron lifetime.

Scaled lifetimes, $`\tau (E)\times (EE_F)^2`$, of hot electrons in Al, as obtained from our full band-structure calculation (solid circles) and from the FEG model with $`r_s=2.07`$ (solid line), are represented in the inset of Fig. 2. In the limit $`EE_F`$, the available phase space for real transitions is simply $`EE_F`$, which yields the $`(EE_F)^2`$ quadratic scaling of very-low-electron energies in a FEG, as predicted by Eq. (23) (dashed line). However, as the energy increases momentum and energy conservation prevents the available phase space from being as large as $`EE_F`$, and the lifetime of electrons in a FEG departures, therefore, from the $`(EE_F)^2`$ scaling. For energies under study, band-structure effects in Al are found to be nearly energy-independent; hence, our calculated lifetimes are found to approximately scale as in the case of electrons in a FEG, and they slightly departure, therefore, from the $`(EE_F)^2`$ scaling. The agreement at $`EE_F3\mathrm{eV}`$ between actual lifetimes and those predicted by Eq. (23) is simply due to the nearly thorough compensation, at these energies, between the departure of this formula from full free-electron-gas RPA calculations and band-structure effects.

Although the energy bands of Al show an overall similarity with the fcc free-electron band structure, in the vicinity of the W-point there are large differences between the two cases \[see Fig. 1\]. At this point, the free-electron parabola opens an energy gap around the Fermi level and splits along the $`WX`$ direction into two bands ($`Z_1`$ and $`Z_4`$) with energies over the Fermi level. We have calculated lifetimes of hot electrons in these bands, with the wave vector along the $`WX`$ direction. The results of these calculations are exhibited in Fig. 2, as a function of energy, by dotted ($`Z_1`$) and long-dashed lines ($`Z_4`$). Although hot electrons in the $`Z_1`$ band have one more channel available to decay along the $`WX`$ direction, the band gap at the $`W`$-point around the Fermi level results in hot electrons living longer on the $`Z_1`$ than on the $`Z_4`$ band. When the hot-electron energy is well above the Fermi level ($`EE_F>4\mathrm{eV}`$), both $`Z_1`$ and $`Z_4`$ lifetimes nearly coincide with the average values represented by solid circles. We have evaluated hot-electron lifetimes along other directions of the wave vector, and have found that differences between these results and average lifetimes are not larger than those obtained along the $`WX`$ direction. This is in disagreement with the calculations reported by Schöne et al. In particular, the bending of the hot-electron lifetime along the WL direction at $`1\mathrm{eV}`$ reported in Ref. is not present in our calculations. The origin of this discrepancy is the crossing near the Fermi level between bands $`Q_+`$ and $`Q_{}`$ along the WL direction reported in Ref.. This crossing is absent in the present \[see Fig. 1\] and previous self-consistent band-structure calculations, which all show that at the $`W`$-point of the Al band structure the level $`W_2^{}`$ is below $`W_1`$.

### B Magnesium

In Fig. 3 we show the band structure of hexagonal closed-packed (hcp) magnesium. There is a close resemblance for energies $`E<E_F`$ between this band structure and that of free electrons, though the free-electron parabola now splits near the Fermi level along certain symmetry directions. As a result, the energy-loss function, $`\mathrm{Im}[ϵ_{𝐆,𝐆^{}}^1(𝐪,\omega )]`$, of this material is approximately well described within a free-electron model, and band-structure effects on hot-electron lifetimes enter mainly, as in the case of Al, through the sensitivity of hot-electron initial and final states on the band structure of the crystal.

Our ab initio calculation of the average lifetime $`\tau (E)`$ of hot electrons in Mg, as obtained from Eq. (17) with full inclusion of crystalline local-field effects, is presented in Fig. 4 by solid circles, together with the lifetime of hot electrons in a FEG with the electron density equal to that of valence electrons in Mg ($`r_s=2.66`$). As in the case of Al, we have found that local-field corrections are negligible for electron energies under study.

Scaled lifetimes of hot electrons in Mg, as obtained from our full band-structure calculations (solid circles) and from the FEG model with $`r_s=2.66`$ (solid line), are represented in the inset of Fig. 4. We note that actual lifetimes in this material scale with energy approximately as in the case of electrons in a FEG, thereby slightly deviating from the $`(EE_F)^2`$ scaling predicted by Eq. (23) (dashed line). Because of splitting of the band structure over the Fermi level new decay channels are opened, not present in the case of a FEG, and band-structure effects tend, therefore, to decrease the lifetime of hot electrons in Mg by a factor of $`0.75`$. Since the splitting of the band structure of Mg is not as pronounced as that of Al, the departure of actual lifetimes from those of electrons in a FEG is found to be smaller in Mg than in Al.

### C Beryllium

Among the so-called simple metals, with no $`d`$ bands, beryllium presents distinctive features in that its band structure \[see Fig. 5\] exhibits the largest departure from free-electron behaviour. Both Be and Mg have hcp crystal structure and two conduction electrons per atom. Nevertheless, the electronic structure of Be is qualitatively different from that of Mg, the Be band gaps at points $`\mathrm{\Gamma }`$, $`H`$, and $`L`$ being much larger than those in Mg. Also, the Be band gaps are located on both sides of the Fermi level, and the density of states (DOS) of this material falls to a sharp minimum near the Fermi level.

Our band-structure calculation of the average lifetime $`\tau (E)`$ of hot electrons in Be is shown in Fig. 6 by solid circles, as obtained from Eq. (17). The lifetime of hot electrons in a FEG with the electron density equal to that of valence electrons in Be ($`r_s=1.87`$) is represented in the same figure by a solid line. In the inset, the corresponding scaled calculations are plotted, together with the results obtained from Eq. (23) (dashed line). It can be seen that large deviations from the FEG calculation occur for electron energies near the Fermi level ($`EE_F<3\mathrm{eV}`$), especially at $`EE_F1.4`$ and $`1.8\mathrm{eV}`$ where the presence of band gaps at points $`\mathrm{\Gamma }`$ and $`L`$ plays a key role. We note that the deep departure from free-electron behaviour of the beryllium DOS near the Fermi level tends to increase the inelastic lifetime of all excited Bloch states. Furthermore, actual lifetimes strongly deviate from the $`(EE_F)^2`$ scaling predicted within Fermi-liquid theory. This deviation comes from the contribution to the average lifetime due to Bloch states near the points $`\mathrm{\Gamma }`$ and $`L`$ with energies close to the energy gap.

At the $`\mathrm{\Gamma }`$-point, the free-electron parabola opens a wide energy gap around the Fermi level and splits along the $`\mathrm{\Gamma }K`$ and $`\mathrm{\Gamma }M`$ directions into two bands, $`T_2/T_4`$ and $`\mathrm{\Sigma }_1/\mathrm{\Sigma }_3`$, respectively. The results of our calculated lifetimes of hot electrons in bands $`T_2`$ and $`T_4`$, with the wave vector along the $`\mathrm{\Gamma }K`$ direction, are plotted in Fig. 7 by short-dashed and long-dashed lines, respectively. For comparison, the average lifetime of hot electrons in real beryllium and in a FEG with $`r_s=1.87`$ are also plotted in this figure by solid circles and by a solid line, respectively. At very-low electron energies ($`EE_F<1\mathrm{eV}`$), interband transitions yield lifetimes of hot electrons in the $`T_2`$ band that are below those of electrons in a FEG, as in the case of Al and Mg. However, at higher energies the coupling with lower lying flat bands becomes small, and lifetimes of electrons in this ($`T_2`$) band are found to be above the FEG prediction. Lifetimes of hot electrons in the $`T_4`$ band are also, at very-low electron energies ($`EE_F<1.4\mathrm{eV}`$), below those of electrons in a FEG. Nevertheless, at energies of $`1.4\mathrm{eV}`$ the presence of the band gap at $`\mathrm{\Gamma }`$ yields very long lifetimes, especially at the level $`\mathrm{\Gamma }_4^{}`$.

We have calculated hot-electron lifetimes in bands $`\mathrm{\Sigma }_1`$ and $`\mathrm{\Sigma }_3`$, with the wave vector along the $`\mathrm{\Gamma }M`$ direction, and have found results that are similar to those obtained for electrons in bands $`T_2`$ and $`T_4`$. Calculations of the lifetime of hot electrons in the $`\mathrm{\Delta }_2`$ band, with the wave vector along the $`\mathrm{\Gamma }A`$ direction, are also shown in Fig. 7 (dotted line). Though this is not a flat band, the presence of the gap at the $`\mathrm{\Gamma }`$-point near the Fermi level results in hot electrons close to the level $`\mathrm{\Gamma }_4^{}`$ living much longer than in the case of a FEG. The combined contribution from hot electrons in bands $`T_4`$, $`\mathrm{\Sigma }_1`$, and $`\mathrm{\Delta }_2`$ is the origin of the enhanced average lifetime (solid circles) at $`EE_F1.4\mathrm{eV}`$, which corresponds to the energy of the level $`\mathrm{\Gamma }_4^{}`$ at the $`\mathrm{\Gamma }`$-point.

A wide band gap is also opened at the $`L`$-point, which originates the enhanced average lifetime at $`EE_F1.8\mathrm{eV}`$. Hence, we have plotted in Fig. 8 the results of our calculated lifetimes of hot electrons in the $`S_1`$ band, with the wave vector along the $`LH`$ direction (dotted line), together with the average lifetime of hot electrons in real Be (solid circles) and in a FEG with $`r_s=1.87`$ (solid line). As in the case of hot electrons in bands $`T_4`$ and $`\mathrm{\Sigma }_1`$, the presence of the band gap at the $`L`$-point yields a very long average lifetime, but now at $`EE_F1.8\mathrm{eV}`$. A similar behaviour is obtained near the $`L`$-point for electrons in the $`R_1R_3`$ band along the $`LA`$ direction, and both bands, $`S_1`$ and $`R_1R_3`$, contribute to the enhanced average lifetime at $`EE_F1.8\mathrm{eV}`$. In Fig. 8 we have also represented calculations of the lifetime of hot electrons in the $`S_1^{}`$ band along the $`HA`$ direction (dashed line). At low energies ($`EE_F<2\mathrm{eV}`$), the presence of the gap at the $`H`$-point leads to hot-electron lifetimes along the $`HA`$ direction that are longer than those of electrons in a FEG, but departure from free-electron behaviour at the $`H`$-point is not as pronounced as at the $`\mathrm{\Gamma }`$ or $`L`$ points. At higher energies, the $`S_1^{}`$ band shows great similarity with the corresponding hcp free-electron band, and lifetimes nearly coincide, therefore, with those obtained within the FEG model.

### D Copper

Copper, the most widely studied metal by TR-2PPE, is a noble metal with entirely filled $`3d`$-like bands. In Fig. 9 we show the energy bands of this fcc crystal. We see a profound difference between the band structure of Cu and that of free electrons. Slightly below the Fermi level, at $`EE_F2\mathrm{eV}`$, we have $`d`$ bands capable of holding 10 electrons per atom, the one remaining electron being in a free-electron-like band below and above the $`d`$ bands. Hence, a combined description of both delocalized $`4s^1`$ and localized $`3d^{10}`$ electrons is needed to address the actual electronic response of this material. The results presented below have been found by keeping all $`4s^1`$ and $`3d^{10}`$ Bloch states as valence electrons in the pseudopotential generation.

Band-structure GW-RPA calculations of the average lifetime $`\tau (E)`$ of hot electrons in Cu are exhibited in Fig. 10 by solid circles, as obtained from Eq. (17) with full inclusion of crystalline local-field effects. The lifetime of hot electrons in a FEG with the electron density equal to that of $`4s^1`$ electrons in Cu ($`r_s=2.67`$) is represented by a solid line. These calculations indicate that the lifetime of hot electrons in Cu is, within RPA, larger than that of electrons in a FEG with $`r_s=2.67`$, this enhancement varying from a factor of $`2.5`$ near the Fermi level ($`EE_F=1.0\mathrm{eV}`$) to a factor of $`1.5`$ for $`EE_F=3.5\mathrm{eV}`$. In order to investigate the role that localized $`d`$ bands play in the decay mechanism of hot electrons, we have also used an ab initio pseudopotential with the $`3d`$ shell assigned to the core. The result of this calculation, displayed in Fig. 10 by a dotted line, shows that it nearly coincides with the FEG calculation; thus, $`d`$-band states play a key role in the hot-electron decay.

We have performed band-structure calculations of Eq. (17) with and without \[see also Eq. (19)\] the inclusion of crystalline local-field corrections, and have found that these corrections are negligible for $`EE_F>1.5\mathrm{eV}`$, while for energies very near the Fermi level neglecting these corrections results in an overestimation of the lifetime of less than $`5\%`$. Therefore, differences between our full band-structure calculations (solid circles) and FEG calculations (solid line) come from the actual DOS available for real excitations, localization, additional screening, and Fermi-surface topology.

First of all, we focus on the role that both DOS and coupling between Bloch states participating in the creation of e-h pairs, i.e., localization \[see Eq. (20)\] play in the hot-electron decay mechanism. Hence, we neglect crystalline local-field effects and present the result of evaluating hot-electron lifetimes from Eq. (19) by replacing initial and final states in $`|B_{if}(𝐪+𝐆)|^2`$ by plane waves and the dielectric function in $`\left|ϵ_{𝐆,𝐆}(𝐪,\omega )\right|^2`$ by that of a FEG with $`r_s=2.67`$. If we further replaced $`\mathrm{Im}\left[ϵ_{𝐆,𝐆}(𝐪,\omega )\right]`$ by that of a FEG, then we would obtain the FEG calculation represented by a solid line. The impact of the actual DOS below the Fermi level may be described by simply replacing the one-electron Bloch states in Eq. (20) by plane waves but keeping the actual number of states available for real excitations. The result of this calculation is represented in Fig. 10 by a dashed line. This result is very close to that reported by Ogawa et al, though these authors approximated the FEG dielectric function in $`\left|ϵ_{𝐆,𝐆}(𝐪,\omega )\right|^2`$ within the static Thomas-Fermi model.

It is clear from Fig. 10 that the actual DOS available for real transitions yields lifetimes that are shorter than those obtained in a FEG model, especially for $`EE_F>2\mathrm{eV}`$ due to opening of the $`d`$-band scattering channel dominating the DOS with energies $`2\mathrm{eV}`$. However, if one takes into account, within a full description of the band structure of the crystal in the evaluation of $`\mathrm{Im}\left[ϵ_{𝐆,𝐆}(𝐪,\omega )\right]`$, the actual coupling between initial and final states avaliable for real transitions, then one obtains hot-electron lifetimes which lie, at very-low electron energies ($`EE_F<2.5\mathrm{eV}`$) just above the FEG curve \[see open circles in Fig. 1 of Ref.\]. This enhancement of the lifetime, even at energies below the opening of the $`d`$-band scattering channel, is due to the fact that states just below the Fermi level have a small but significant $`d`$ component, thus being more localized than pure $`sp`$ states.

The combined effect of DOS and localization, which enters through the imaginary part of the dielectric matrix $`\mathrm{Im}\left[ϵ_{𝐆,𝐆^{}}(𝐪,\omega )\right]`$, increases the lifetime of hot electrons with energies $`EE_F<2.5\mathrm{eV}`$ \[see open circles in Fig. 1 of Ref.\]. As for the departure of hot-electron initial and final states from free-electron behaviour, entering through the coefficients $`B_{if}(𝐪+𝐆)`$, we have found that it yields hot-electron lifetimes that are strongly directional dependent, Fermi-surface shape effects tending to decrease the average inelastic lifetime of very-low-energy electrons ($`EE_F<2.5\mathrm{eV}`$) \[see Ref.\]. Furthermore, the combined effect of DOS and localization, on the one hand, and Fermi-surface shape effects, on the other hand, nearly compensate. Consequently, large differences between hot-electron lifetimes in real Cu and in a FEG with $`r_s=2.67`$ are mainly due to a major contribution from $`d`$ electrons participating in the screening of electron-electron interactions, which is accounted through the factor $`\left|ϵ_{𝐆,𝐆}(𝐪,\omega )\right|^2`$ in Eq. (19).

The Fermi surface of Cu is greatly flattened in certain regions, showing a pronounced neck in the direction $`\mathrm{\Gamma }L`$. Thus, the isotropy of hot-electron lifetimes in a FEG disappears in this material. While flattening of the Fermi surface along the $`\mathrm{\Gamma }K`$ direction is found to decrease the hot-electron lifetime by a factor that varies from $`15\%`$ near the Fermi level ($`EE_F=1\mathrm{eV}`$) to $`5\%`$ for $`EE_F=3.5\mathrm{eV}`$ \[see also Ref.\], the lifetime of hot electrons with the wave vector along the necks of the Fermi surface, in the $`\mathrm{\Gamma }L`$ direction, is found to be much longer than the average lifetime. We have calculated hot-electron lifetimes in the $`\mathrm{\Lambda }_1`$ band, with the wave vector along the $`\mathrm{\Gamma }L`$ direction, and have found the lifetime of hot electrons at the $`L_1`$ level with $`EE_F=4.2\mathrm{eV}`$ to be longer than the average lifetime at this energy by $`80\%`$.

A comparison between our calculated hot-electron lifetimes in Cu and those determined from most recent TR-2PPE experiments was presented in Ref.. At $`EE_F<2\mathrm{eV}`$, our calculations are close to lifetimes recently measured by Knoesel et al in the very-low energy range. At larger electron energies, good agreement between our band-structure calculations and experiment is obtained for Cu(110), the only surface with no band gap in the $`𝐤_{}=0`$ direction.

## IV Conclusions

We have presented full GW-RPA band-structure calculations of the inelastic lifetime of hot electrons in Al, Mg, Be, and Cu, and have demonstrated that decay rates of low-energy excited electrons strongly depend on the details of the electronic band structure. Though the dependence of hot-electron lifetimes in Al and Mg on the direction of the wave vector has been found not to be large, in the case of Be and Cu hot-electron lifetimes have been found to be strongly directional dependent. Furthermore, very long lifetimes at certain points of the BZ in Be yield average lifetimes in this material which strongly deviate from the $`(EE_F)^2`$ scaling predicted within Fermi-liquid theory.

As far as band-structure effects on hot-electron energies and wave functions are concerned, we have found that both splitting of the band structure and the presence of band gaps over the Fermi level play an important role in the e-e decay mechanism. In Al and Mg, splitting of the band structure is found to yield electron lifetimes that are smaller than those of electrons in a FEG. On the other hand, large deviations of the band structure of Be along certain symmetry directions from the free-electron model near the Fermi level result in a strong directional dependence of hot-electron lifetimes in this material.

As for the presence of band-structure effects on the creation of e-h pairs, there are contributions from the actual DOS available for real transitions, from localization, i.e., the actual coupling between electron and hole states, and from screening. The combined effect of DOS and localization is found not to be large, even in the case of a noble metal like Cu with $`d`$ bands. However, large differences between hot-electron lifetimes in Cu and in a FEG with the electron density equal to that of valence ($`4s^1`$) electrons are found to be due to a major contribution from $`d`$ electrons participating in the screening of e-e interactions.

Crystalline local-field corrections in these materials have been found to be small for hot-electron energies under study.

## V Acknowledgments

We would like to thank A. G. Eguiluz for stimulating discussions. We also acknowledge partial support by the University of the Basque Country, the Basque Hezkuntza, Unibertistate eta Ikerketa Saila, and the Spanish Ministerio de Educación y Cultura.


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## Acknowledgments

This work was supported in part by the United States Department of Energy under contract numbers DE–AC03–76SF00515, and DE-FG03-97ER4104 and by a grant from the U.S.-Israel Binational Science Foundation. We appreciate the hospitality of the CSSM in Adelaide where some of this work was performed. We thank W. Melnitchouk, S. Rock, M. Strikman, and especially G. van der Steenhoven, for useful discussions.