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# Nuclear Inelastic X-Ray Scattering of FeO to 48 GPa

## Abstract

The partial density of vibrational states has been measured for Fe in compressed FeO (wüstite) using nuclear resonant inelastic x-ray scattering. Substantial changes have been observed in the overall shape of the density of states close to the magnetic transiton around 20 GPa from the paramagnetic (low pressure) to the antiferromagnetic (high pressure) state. Our data indicate a substantial softening of the aggregate sound velocities far below the transition, starting between 5 and 10 GPa. This is consistent with recent radial x-ray diffraction measurements of the elastic constants in FeO. The results indicate that strong magnetoelastic coupling in FeO is the driving force behind the changes in the phonon spectrum of FeO.

The study of the electronic and magnetic properties of simple transition-metal compounds is an important topic in diverse fields ranging from solid-state physics to Earth sciences. Iron oxide FeO (wüstite) belongs to the group of highly correlated transition metal oxides, being an archetypal insulating antiferromagnetic material at zero temperature. NiO, CoO, MnO fall in the same group of materials, which are still not well understood by theory. They also present a challenge to experimentalist because the predicted high pressure transformations in these materials (metallization, high-spin to low-spin transitions) may occur at extreme pressures ( e. g. $`>`$ 100 GPa). FeO stands out from this group of materials in the sense that it is a possible major constituent of the Earth’s lower mantle and core, thus its pressure and temperature dependent properties are very important for the understanding of the Earth’s interior. Here we present a study of the vibrational density of states of isotope-enriched Fe0.947O using high-resolution nuclear resonant inelastic x-ray scattering. We observe changes in the density of states that are consistent with the softening of the aggregate shear sound wave velocity of wüstite under pressure , which we associate with the phase transition from the cubic paramagnetic phase to the rhombohedrally distorted antiferromagnetic phase stable at higher pressures. We show that the phonon density of states is affected by magnetoelastic coupling between phonon and spin subsystems in FeO.

Experiments were performed at the synchrotron beamline SRI-CAT 3ID of the Advanced Photon Source (APS), Argonne National Laboratory. The details of the diamond cell and the experimental setup are reported elsewhere . The sample was $``$ 25 $`\mu `$m in diameter (loaded without pressure medium), and diamonds with flat 400 $`\mu `$m culets were used. The maximum counting rate in the phonon wing ranged from 10 cps at 0.9 GPa to 2 cps at 48 GPa. The measured spectra, i. e., count rate as a function of the energy difference between the incident photon energy and the nuclear transition energy, $`I(\mathrm{\Delta }E)`$, were converted to phonon DOS profile according to the data analysis procedure described by Hu et al. . Typically, 10-20 DOS spectra (one hour/spectrum) at the same pressure were summed together. The pressure was measured using the ruby fluorescence line and a nonhydrostatic pressure scale .

Experimental data are presented in Fig.1. In Fig.2 we compare the phonon DOS of FeO as derived from neutron scattering  and the partial phonon DOS of Fe at 0.9 GPa from our measurements. High frequency oxygen modes are absent from our data, indicating that Fe vibrational amplitude is negligible at oxygen vibrational frequencies. One apparent feature of the experimental data is an inelastic peak at small energy transfers which develops at 10 GPa, and persists through almost the entire pressure range of the present experiment to 48 GPa. It is most pronounced near 16 and 20 GPa, which is exactly the pressure range of the reported transition from the paramagnetic rock-salt-type structure to the antiferromagnetic rhombohedral structure . The transition is very sensitive to (nonhydrostatic) stress conditions ; for example, the splitting of the (111) diffraction line being smeared between 10 to 18 GPa if no pressure medium was used, and occuring around 16 GPa  to 17 GPa  under quasihydrostatic conditions.

The calculated partial density of states weighted by the square of the energy E2 is plotted versus energy in Fig.3. In Fig.3, the density of states in the Debye approximation would be a straight horizontal line, related to the aggregate sound velocity of the material . The apparent feature of our data is the pronounced softening of the low energy vibrational spectrum. The resolution of the present measurements (2.4 meV) does not allow us to follow the softening to the low frequency region, where most static and ultrasonic measurements are performed. However, this behavior suggests large effects on the static elastic constants at the Nèel transition.

The temperature dependence of the elastic constants of Fe0.92O at ambient pressure was investigated in detail by Sumino et al. . Substantial softening of the shear constant C44 was found close to the Nèel transition. Similar anomalies have also been observed in MnO (softening of C44) . The magnetic structure studies  by neutron scattering have shown that the Mn spins align ferromagnetically within a given (111) plane, and these planes are stacked antiferromagnetically in the $`<`$111$`>`$ direction. Similarly, FeO has the same magnetic structure, with magnetic moments pointing in the $`<`$111$`>`$ direction. At temperatures below the Nèel temperature MnO undergoes a lattice contraction along the antiferromagnetic stacking direction $`<`$111$`>`$ . The distortion in FeO has different sign, the elongation along the body diagonal. The magnetic system breaks into multiple domains (called T domains) corresponding to the antiferromagnetic stacking along the four possible $`<`$111$`>`$ directions within the crystal. Experimental  and theoretical  studies in MnO invoke exchange-striction effects to explain the character of the transition. The results of these studies can be summarized as follows. The energy balance is determined by minimizing the sum of magnetic exchange energy and elastic energy, resulting in a rhombohedral distortion

$$\mathrm{\Delta }=z_1NJ_1ϵ_1S^2/24C_{44}$$
(1)
Here $`\mathrm{\Delta }`$ denotes the distortion of trigonaly deformed cube corner angles $`\frac{1}{2}\pi \pm \mathrm{\Delta }`$, $`C_{44}`$ is the shear constant, $`J_1`$ is the exchange integral for the nearest neighbors, $`z_1`$ is the number of the nearest neighbors, $`ϵ_1=r\delta lnJ_1/\delta r`$, and $`S^2=<S_iS_j>_{nn}^p<S_iS_j>_{nn}^a`$ is a correlation function for nearest neighbors with parallel spins (residing within the same $`<`$111$`>`$ plane) and antiparallel spins in neighboring $`<`$111$`>`$ planes. The numerical value of $`\mathrm{\Delta }`$ is about 0.5 degree at 4 K in MnO. Actually, according to Bartel,  $`\mathrm{\Delta }`$ is proportional to the sublattice magnetization and is a sensitive measure of the order parameter of the magnetic phase.

However, FeO and CoO have much larger volume anomalies below TN and their magnetic properties according to Kanamori  cannot be described by the theory developed by Lines and Bartel . In a crystal field of cubic symmetry, the orbital degeneracies of Fe2+ and Co2+ are not completely removed, and the residual orbital angular momenta contribute to the energy balance through spin-orbit coupling and the direct effect of orbital magnetic moments, resulting in observable magnetostriction effects. Substantial contribution to the magnetostriction effects in FeO is due to the magnetic anisotropy energy . Kanamori  calculated the equlibrium strain components for FeO resulting from magnetostriction. He used the general formulation derived by Kittel for cubic systems  (all $`C_{ij}`$’s are cubic elastic constants, $`B_1`$ and $`B_2`$ are cubic magnetoelastic constatnts):

$`e_{ii}=B_1\left((1/3)\alpha _i^2\right)/(C_{11}C_{12}),`$ (2)
$`e_{ij}=B_2\alpha _i\alpha _j/C_{44}`$ (3)
where $`\alpha _i`$ are direction cosines of the magnetization. Kanamori’s treatment leads to an elongation along  diagonal in FeO, which agrees with experimental results . From the experiments on FeO at 95 K  one derives a rhombohedral angle of 59 32’, or exy=0.705 %. To estimate the rhombohedral distortion resulting from the exchange interaction (Eq.1) in FeO, we need reliable information about the exchange integrals and their dependence on the lattice parameter, which to our knowledge is not available at the moment. The experimental values of distortion  seem to be quite close to the Kanamori’s calculation. Moreover, rhombohedral distortion is enhanced at high pressures , indicating increasing B2 in FeO under pressure.

The cubic constant $`B_2`$ is responsible for the magnetoelastic coupling between the phonon and the magnon branches, and our results on the enhanced phonon density of states are directly related to the magnetoelastic coupling in FeO. The expression for phonon dispersion including the magnetoelastic coupling follows from the equations of motion for the magnetic moment :

$$(\omega ^2\omega _m^2)(\omega ^2\omega _s^2)\frac{gk^2B_2^2\mathrm{\Omega }}{2\rho M_0}=0$$
(4)
Here $`\omega _s`$ is the frequency of sound wave, and $`\omega _m^2=\mathrm{\Omega }gM_0(\beta +\alpha k^2)`$ is the spin wave frequency in the absence of magnetoelastic coupling; $`\rho `$ is the density of the material, $`M_0`$ is the magnitude of the magnetic moment of one sublattice, $`\mathrm{\Omega }=gM_0(\beta +2\gamma )`$. The parameters $`\alpha `$, $`\gamma `$, and $`\beta `$ are related to the exchange interactions and magnetic anisotropy in the material , $`g`$ is the gyromagnetic ratio, and $`k`$ is a wavevector.

The calculated dispersion relations for FeO at 28 GPa with magnetoelastic coupling included  are shown in Fig.4a (estimated at T=295 K), corresponding sound velocities are shown in Fig.4b. Dispersion relations (Fig.4a) change by less than 1 meV, well within the resolution of neutron inelastic scattering experiment. However, as is evident from Fig.4b, the effect on the sound velocities is more pronounced, being almost 20-30 % within the energy transfer range up to 5 meV. This agrees reasonably well with the enhancement of the density of states which we observe in our experiment (Fig.3). Quantitave agreement may be sought along the lines of more elaborated theoretical models, similar to Ref..

At present we do not have enough experimental information and theoretical understanding to better constrain the magnetoelastic coupling at T/TN $``$ 1. However, as follows from our observations, the effect is most pronounced close to the Néel transition. Our observations support the Mössbauer measurements, where the magnetic transition was observed starting from 8 GPa under nonhydroctatic conditions. The reason is that uniaxial strain along the body diagonal may induce magnetic moments well below the transition point determined under hydrostatic conditions (17 GPa). This is consistent with the notion that this second order phase transition is smeared by the external field (uniaxial strain), which is proportional to the order parameter of the broken symmetry phase .

In summary, we have observed substantial softening of the density of states at energy transfers below 10 meV in FeO at pressures close to 15-20 GPa, which persists in its antiferromagnetic phase up to 40-48 GPa. We relate the observed softening to the effect of the magnetoelastic coupling in this material. The theoretical estimates  show that both rhombohedral distortion and magnetoelastic coupling include substantial contributions from the magnetic anisotropy energy in FeO, which arises from the spin-orbit coupling in the orbitally degenerate ground state . Further experimental work is required to clarify the effect of exchange-driven magnetoelastic contribution.

Portions of this work was performed at GSECARS, which is supported by the NSF, W.M. Keck Foundation and the USDA. The APS is supported by the DOE under Contract No. W-31-109-Eng-38. V. V. S. acknowledges Ron Cohen for bringing to his attention Ref..


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# Deconstructing Gaugino Mediation

## 1 Introduction

Gauge mediated supersymmetry breaking  (GMSB) with a messenger scale much lower than the Planck scale is an elegant solution to the supersymmetric (SUSY) flavor problem. It relies on the fact that standard model (SM) gauge couplings are flavor universal and therefore all gauge-loop contributions to soft masses produce a degenerate spectrum.

Gaugino mediated supersymmetry breaking (g̃MSB)  is another simple solution to the SUSY flavor problem. It uses locality to forbid flavor violating scalar masses by putting matter of the minimal supersymmetric standard model (MSSM) on a brane separated in an extra dimension from a brane on which SUSY is broken . Putting gauge superfields in the bulk allows the gauginos to acquire a mass from direct interactions with the SUSY-breaking brane. The renormalization group (RG) is responsible for scalar masses at the low scale and again it is the universality of gauge couplings which make the generations degenerate.

In this letter, we describe a simple model of “deconstructed” gaugino mediation. In  it was shown that extra dimensional gauge theories can be regularized by a lattice of gauge groups connected by “link” fields in bifundamental representations of neighboring groups which break the “chain” down to the diagonal subgroup. At low energies, these models look identical to extra-dimensional theories as one finds the correct spectrum of Kaluza-Klein modes. Using this framework, intuition gained from extra dimensions can now be applied to constructing interesting four-dimensional theories . In , g̃MSB was translated into this language and shown to reproduce the same spectrum, from a completely four-dimensional theory. Some of the results of our paper overlap with .

We discuss a particularly simple version of deconstructed gaugino mediation with only two gauge groups in the chain. We examine the model in the limit of $`M_{mess}v`$, where $`M_{mess}`$ is the messenger scale and $`v`$ is the scale at which the chain is broken to the diagonal subgroup. We find that this allows sufficient separation of SUSY breaking and MSSM matter fields to suppress scalar masses as in gaugino mediation.

The model has a striking signature: gaugino masses unify at the GUT scale whereas all MSSM scalar masses run to zero at an intermediate scale.

In the next section we describe the model and derive the superpartner spectrum. In Section 3, we discuss threshold corrections to scalar masses and show they are negligible compared to that from running. In Section 4 we show that gauge coupling unification is preserved in this model. The final section is reserved for concluding remarks.

## 2 The model

The model consists of a “visible” sector with the standard model gauge group and the MSSM matter fields. The visible sector communicates with a “hidden” sector gauge group through “link” fields which are charged under both. We assume that SUSY is broken dynamically and SUSY breaking is mediated to the hidden sector by messenger fields which carry hidden sector gauge quantum numbers (see Figure 1).

A summary of the dynamics of the model, from the highest scale to the lowest, is as follows: SUSY breaking is mediated to the hidden sector gauge group at the scale $`M`$, the mass of the messengers. At this scale, hidden sector gauginos obtain a mass at one loop and the link chiral superfields pick up masses at two loops. The MSSM fields also obtain SUSY breaking masses at this scale, but they are suppressed by additional loop factors and are therefore negligible. At the scale $`v`$ the link fields get their vacuum expectation values (vevs) and break the visible and hidden sector gauge groups to diagonal $`SU(3)\times SU(2)\times U(1)`$. The only fields lighter than this scale are the matter and gauge fields of the MSSM.

The MSSM gauge fields and gauginos which remain after the symmetry breaking are linear combinations of the visible and hidden sector fields. The gauginos inherit a large SUSY breaking mass from their hidden component at tree level. The MSSM scalar masses are suppressed by loop factors compared to the gaugino mass at this scale, thus reproducing the pattern of soft masses characteristic of gaugino mediation with compactification scale $`R^1v`$.

We now present the model in detail. The visible sector gauge group is $`G_{vis}=SU(3)\times SU(2)\times U(1)`$ (we discuss unification in Section 4). MSSM matter fields are charged under this gauge group with the usual quantum numbers. The hidden sector gauge group is $`SU(5)_{hid}`$. Link fields $`L+\overline{L}`$ transform as $`(5,\overline{5})+(\overline{5},5)`$ under $`G_{vis}\times SU(5)_{hid}`$, where we use $`SU(5)`$-GUT notation to denote the representations of $`G_{vis}`$. The messenger fields $`T+\overline{T}`$ transform as $`5+\overline{5}`$ under $`SU(5)_{hid}`$ only. The superpotential is

$$W=W_{\mathrm{MSSM}}+XT\overline{T}+S(\frac{1}{5}\mathrm{tr}L\overline{L}v^2)+\mathrm{tr}LA\overline{L},$$
(1)
where $`X=M+\theta ^2F`$ is the spurion which encapsulates the SUSY breaking sector and $`A`$ is an adjoint of $`SU(5)_{hid}`$. Meanwhile, $`W_{\mathrm{MSSM}}`$ is the usual MSSM superpotential with Yukawa couplings and the $`\mu `$-term. The second term gives the messengers a SUSY violating mass when $`X`$ is replaced by its vev. The third term forces vevs for the links $`L`$, $`\overline{L}`$ at the scale $`v`$ and breaks $`G_{vis}\times SU(5)_{hid}`$ to the diagonal $`SU(3)\times SU(2)\times U(1)`$. One linear combination of the link fields get eaten by gauge fields of the broken generators and the other gets a mass due to the fourth term. No light fields charged under the MSSM gauge group remain at scales lower than $`v`$.

At the messenger scale $`M`$, the hidden gauginos get their masses at one loop as in GMSB: $`m_{1/2}^{hid}=(\alpha _{hid}/4\pi )(F/M)`$ (we have assumed only one pair of messengers). The link fields $`L,\overline{L}`$ get scalar masses at two loops. The gauginos of $`G_{vis}`$ are effectively massless at this scale (gaugino “screening” ), and the leading contribution to scalar masses are four-loop diagrams such as the one in Figure 2(a).

Between the scales $`M`$ and $`v`$, the soft terms run via the renormalization group. The visible sector soft masses remain negligible if $`M>>v`$. In principle, there could be a one-loop contribution to the MSSM scalar masses from the hypercharge D-term, however the D-term vanishes at leading order in our model because the link field scalar masses are universal.

At the scale $`v`$, $`G_{vis}\times SU(5)_{hid}`$ is broken to the diagonal $`SU(3)\times SU(2)\times U(1)G_{\mathrm{MSSM}}`$. The gauge couplings $`g_i`$ of the remaining groups are given by $`1/g_i^2=1/(g_{i,vis})^2+1/(g_{hid})^2`$. One linear combination of the gauginos is heavy due to the super-higgs mechanism. The light gaugino, $`\lambda _{\mathrm{MSSM}}`$ is the linear combination

$$\frac{g_{vis}}{\sqrt{g_{vis}^2+g_{hid}^2}}\lambda _{hid}\frac{g_{hid}}{\sqrt{g_{vis}^2+g_{hid}^2}}\lambda _{vis}.$$
(2)
The soft gaugino masses for the three MSSM gauge groups are

$$m_i=\frac{\alpha _i}{\alpha _{hid}}m_{1/2}^{hid}=\frac{\alpha _i}{4\pi }\frac{F}{M}$$
(3)
which is identical to that expected from canonical GMSB.

As discussed, the scalar masses above the scale $`v`$ are negligible. At the threshold $`v`$ small scalar masses are generated from integrating out the massive fields $`L,\overline{L}`$ and the heavy gaugino. The dominant contribution arises from a one-loop diagram with gauginos and gives $`(\alpha /4\pi )(m_{1/2}^{hid})^2`$. This is smaller than the weak scale scalar masses generated from the renormalization group by a loop factor. We discuss theoretical issues regarding the threshold corrections to the scalar masses in more detail in the following section.

We see from Eq. (3) that gaugino masses appear to unify at the GUT scale. On the other hand, if one runs the “observed” scalar masses to higher scales one would discover that they all vanish at an intermediate scale $`v`$.

## 3 Scalar masses from threshold corrections

In this section we give a more careful treatment of the calculation of the MSSM scalar masses in order to show that they are really suppressed at the scale $`v`$. We begin by integrating out the messenger fields $`T+\overline{T}`$ and write an effective Lagrangian valid below the scale $`M`$. At one-loop we get the gaugino mass

$$\frac{\alpha _{hid}}{4\pi }d^2\theta \mathrm{log}(X)W_\alpha W^\alpha \frac{\alpha _{hid}}{4\pi }\frac{F}{M}\lambda \lambda .$$
(4)
This is the only $`d^2\theta `$ term which can be generated by the non-renormalization theorem. However, the diagram also generates higher-dimensional Kähler terms such as

$$\frac{\alpha _{hid}}{4\pi }d^4\theta \frac{X^{}X}{M^4}W_\alpha D^2W^\alpha \frac{\alpha _{hid}}{4\pi }\frac{F^{}F}{M^4}\lambda \overline{)}\lambda ,$$
(5)
a SUSY violating renormalization of the gaugino kinetic terms. This is the leading operator, others are suppressed by more powers of $`M`$ and decouple rapidly at lower energies.

The link scalars first couple to supersymmetry breaking at two loops and obtain the usual gauge-mediated scalar mass $`(\alpha /4\pi )^2F^2/M^2`$. The leading diagram contributing to MSSM scalar masses at this scale is the four-loop diagram shown in Figure 2(a). For loop momenta which are large compared to $`v`$ this diagram yields $`(\alpha _{vis}/4\pi )^2(\alpha _{hid}/4\pi )^2F^2/M^2`$. Note that in the limit of either one of the two gauge couplings becoming large ($`4\pi `$), this scalar mass contribution is important and the model does not reproduce the gaugino mediation spectrum.

Thus, above the scale $`v`$ MSSM scalar masses are suppressed by two loop factors relative to the square of the gaugino masses. One might worry that after breaking of the gauge groups to the diagonal much larger contributions to the scalar masses may arise from the diagram in Figure 2(b). Because of the large number of propagators the diagram is UV-finite, it is dominated by loop momenta of order $`v`$ where we can estimate its contribution to be $`v^2/M^2(\alpha _{hid}\alpha _{vis}/16\pi ^2)F^2/M^2`$. Thus this contribution is suppressed by the separation of scales between the messenger mass and the link vevs. In the opposite limit, $`v\stackrel{>}{_{}}M`$, the suppression disappears and the diagram reduces gives the usual two-loop scalar masses of canonical GMSB. This should be no surprise because for $`vM`$ the breaking to the diagonal group occurs first; below the scale $`v`$ the model is just canonical gauge mediation.

Finally, there is one more contribution to MSSM scalar masses from loop momenta near $`v`$. It come from the same diagram in Figure 2(b). but with two gaugino mass insertions. This gives $`(\alpha _{vis}/4\pi )(\alpha _{hid}/4\pi )^2F^2/M^2`$ which smoothly matches onto the contribution in the MSSM below $`v`$.

In summary, we find that as long as the scales $`M`$ and $`v`$ are well separated our model reproduces the gaugino mediation spectrum. The MSSM scalar masses at the high scale are suppressed relative to gaugino masses by the smaller of a loop factor or the ratio $`(v/M)^2`$.

## 4 Gauge coupling unification

We now turn to the issue of gauge coupling unification. So far, we have only dealt with energies below the unification scale. Therefore, we assumed that $`G_{vis}=SU(3)\times SU(2)\times U(1)`$. If coupling unification is not a numerical accident, then at the unification scale $`G_{vis}`$ must be unified. For simplicity, we will take $`G_{vis}=SU(5)`$ at that scale. The product group structure turns out not to affect the unification scale.

Below the scale $`v`$, the gauge couplings evolve according to ordinary MSSM equations. At $`v`$, $`G_{vis}`$ and $`G_{hid}`$ are no longer broken to their diagonal subgroup and the couplings evolve independently. Thus, the Standard Model gauge couplings need to be matched onto the new theory. At tree level we have

$$\frac{1}{g_i^2}=\frac{1}{g_{i,vis}^2}+\frac{1}{g_{hid}^2},$$
(6)
where $`g_i`$ indicate MSSM couplings just below $`v`$, and $`g_{i,vis}`$ corresponding $`G_{vis}`$ couplings just above $`v`$. All $`1/g_i^2`$ are shifted by the same amount, $`1/g_{hid}^2`$. Therefore, the differences between the gauge couplings remain unchanged across the threshold (this fact is also exploited in ).

Above $`v`$, the link fields $`L,\overline{L}`$ also contribute to the running in addition to the gauge bosons. The link fields form complete multiplets of $`SU(5)_{vis}`$, so they do not alter the relative running of the gauge couplings. Since the differences of couplings are not changed across the threshold $`v`$ and continue to evolve at the MSSM rate, the unification scale for $`G_{vis}`$ is unchanged and equals to $`210^{16}\mathrm{GeV}`$.

## 5 Conclusions

In this letter we present a simple, calculable, renormalizable four-dimensional theory of SUSY breaking and mediation which reproduces the superpartner spectrum of gaugino mediation. There are no branes, troublesome moduli or dynamical assumptions. The superpartner masses are generated from field theory dynamics. They are flavor preserving and insensitive to uncertainties stemming from our incomplete understanding of quantum gravity as long as the messenger scale $`M\stackrel{<}{_{}}10^4M_{Planck}`$. As in higher dimensional gaugino mediation the requirements on the SUSY breaking sector are much less stringent than in canonical GMSB, we only require that the gauginos of the hidden sector unsuppressed masses.

The superpartner spectrum is determined by the fact that the MSSM scalar masses vanish at the scale $`vM`$. Weak scale scalar masses are predicted from the RG evolution , and become similar to no-scale  masses when $`v`$ approaches $`M_{GUT}`$. Roughly, one finds that the masses of colored fields are largest while fields with only hypercharge couplings are smallest. Therefore the right-handed sleptons and the Bino are light, with the stau being the lightest MSSM superpartner. This spectrum is preferred by fits to the recent measurement of the muon anomalous magnetic moment . In contrast with minimal gaugino mediation we find that the gravitino is the LSP as in GMSB.

## 6 Acknowledgements

We thank Csaba Csaki and Graham Kribs for useful discussions. DK and WS thank the summer visitor program of the Theory Department at Fermilab for their hospitality. H.-C. Cheng is supported by the Robert R. McCormick Fellowship. We are also supported by the DOE grants DE-FG02-90ER-40560 (HCC, DEK), W-31-109-ENG-38 (DEK), DE-AC02-76CH03000 (MS), DE-FC02-94ER40818 (WS).


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# Numerical study of quantum percolation

In a recent attempt  to describe the metal-insulator transition in CMR manganites we assumed a percolative coexistence of the two competing phases. In the insulating phase doped holes are trapped by local Jahn-Teller or breathing type lattice distortions. The metallic phase consists of itinerant carriers whose hopping amplitude is coupled via double-exchange  to a background of localised spins.

To gain insight into the properties of the latter phase, we study the classical double-exchange model on a site percolated cluster,

$$H=\underset{kl}{}[t_{kl}c_k^{}c_l+\text{H.c.}].$$
(1)
Here $`c_l^{}`$ creates a spinless fermion in the Wannier state at site $`l`$, and the summation is over neighbouring sites on a simple cubic lattice. The matrix element $`t_{kl}`$ is nonzero only between sites of a cluster,

$`t_{kl}`$ $`=`$ $`\mathrm{cos}\frac{\theta _k}{2}\mathrm{cos}\frac{\theta _l}{2}\mathrm{e}^{i(\varphi _k\varphi _l)/2}`$ (3)
$`+\mathrm{sin}\frac{\theta _k}{2}\mathrm{sin}\frac{\theta _l}{2}\mathrm{e}^{i(\varphi _k\varphi _l)/2},`$
where the angles $`\{\theta _l,\varphi _l\}`$ parameterise the background of classical spins. Hence, in the present model there are two types of disorder which cause scattering or localisation of the involved fermions, namely, the random structure of the cluster and the disorder in the hopping matrix elements.

To construct a certain realization of the model (1) with a given probability $`p`$ we choose active sites from a simple cubic lattice. After labelling  the resulting clusters we keep only the largest (or the spanning) one for further calculations. To fix the hopping matrix elements a set $`\{\theta _l,\varphi _l\}`$ is taken from an ensemble of thermalized classical spins in a magnetic field $`h_{\mathrm{eff}}`$. This introduces the parameter $`\lambda =\beta g\mu _Bh_{\mathrm{eff}}`$.

Application of Chebyshev expansion and maximum entropy methods  yields the density of states, shown in Figure 1 for different values of $`p`$ and $`\lambda `$. For the ordered spin background ($`\lambda =\mathrm{}`$) with decreasing $`p`$ a pseudo-gap feature appears close to the band centre, together with a distinct peak at $`E=0`$. The weight $`W`$ of this central peak (left hand inset) increases continuously, and makes up more than 10% of the spectrum close to the classical percolation threshold $`p_c0.3116`$. On the other hand, increasing spin disorder, i.e., decreasing $`\lambda `$, transfers spectral weight to the band centre. It does not seem to affect the weight of the central peak. Of course, both types of disorder reduce the overall bandwidth.

What remains to be clarified is the nature of the involved eigenstates. Our calculations indicate that the states in the band centre show a chequerboard structure and are less localised compared to the rest of the spectrum. Similar behaviour was also found for lower dimensional systems, as discussed in Ref. .

Figure 2 shows the regular part of the optical conductivity,

$$\sigma _{\mathrm{reg}}(\omega )=\frac{1}{N}\underset{m0}{}\frac{|m|j_x|0|^2}{\omega _m}\delta (\omega \omega _m),$$
(4)
with $`\omega _m=E_mE_0`$. The current $`j_x`$ is given by

$$j_x=\underset{kl_x}{}[it_{kl}c_k^{}c_l+\text{H.c.}],$$
(5)
where the summation extends over neighbouring sites in $`x`$-direction only. Considering clusters on a $`10^3`$ site lattice, we calculated the eigenstates of the hopping matrix and summed up the current matrix elements between empty and occupied eigenstates. We assumed zero (electron) temperature and a band filling of $`0.2`$. Clearly, below the classical percolation threshold (panel (a)) we deal with finite size clusters which do not (or rarely) connect the boundaries. Hence, the averaged $`\sigma _{\mathrm{reg}}`$ is rather noisy and approaches zero in the limit $`\omega 0`$. For $`p>p_c`$ (panels (b) and (c)) the curves become smooth, and we obtain a finite dc conductivity. In panel (b) the hump between $`\omega =1`$ and $`2`$ is due to excitations into the central peak. With decreasing $`\lambda `$ it is shifted to lower frequencies, because of the reduced bandwidth. Further studies of the model should clarify whether the quantum percolation threshold  $`p_q>p_c`$ is also visible in the optical conductivity.


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# On the semiclassical theory for universal transmission fluctuations in chaotic systems: the importance of unitarity

## I Introduction

Since the pioneering work of Blümel and Smilansky  the semiclassical $`S`$-matrix  has been used by many authors to study fundamental questions related to quantum chaotic scattering. In recent years the interest in this subject has grown due to the experimental investigation of electronic transport through small devices, such as open quantum dots . At sufficiently low temperatures, these devices preserve quantum coherence and are called mesoscopic. The conductance in transport processes that preserve quantum coherence is directly related to the $`S`$-matrix by the Landauer-Büttiker formula . Since the classical underlying electronic dynamics in quantum dots is believed to be chaotic, these are excellent systems to observe the quantum manifestations of classical chaotic scattering .

One of the central issues in mesoscopic physics is to single out statistical universal properties of quantum systems. In this paper we show that this goal cannot be theoretically achieved using the standard semiclassical $`S`$-matrix approach, since the latter is not able to provide trustworthy results for universal cross-section or conductance correlation functions. We also show that this situation can be fixed by imposing a set of semiclassical sum rules that guarantee unitarity.

For a device connected to reservoirs by two leads, the Landauer-Büttiker formula relates its conductance $`G`$ to the transmission coefficient $`T`$ by the expression $`G=(2e^2/\mathrm{})T`$. In electronic transport, $`T`$ is usually called the dimensionless conductance. When the entrance and exit leads support $`N_1`$ and $`N_2`$ propagating modes or channels, respectively, the transmission $`T`$ reads

$$T(x)=\underset{a=1}{\overset{N_1}{}}\underset{b=N_1+1}{\overset{N}{}}|S_{ab}(x)|^2=\underset{a,b}{}\sigma _{ab}(x),$$
(1)
where we have introduced $`\sigma _{ab}`$, the transition probability (the cross-section, apart from a kinematical factor) from channel $`b`$ in one lead to channel $`a`$ in the other lead. The parameter $`x`$ represents either the energy $`E`$, or an external parameter $`X`$ such as a magnetic field, or both. Without loss of generality we restrict our discussion to the case where $`N_1=N_2=N/2M`$.

The original problem of conductance fluctuations in a mesoscopic device is now cast into a more generic one of transmission fluctuations of a quantum process where a particle is chaotically scattered. Thus, this discussion is also of interest for transmission experiments with irregular microwave cavities, “chaotic” atoms and nuclei. Our goal is to use the semiclassical theory to describe the statistical properties of the transmission as the parameter $`x`$ is varied. This information is contained in the average value of $`T`$ (a two-point statistical measure of the $`S`$-matrix elements) and in its autocorrelation function (a four-point function), defined as

$$(T,T^{})T(x)T(x^{})T(x)T(x^{}).$$
(2)
The average is taken over $`x`$ and $`x^{}`$ keeping the difference $`|xx^{}|`$ fixed. The transmission autocorrelation function is directly related to the covariances of the transition probabilities

$$(T,T^{})=\underset{a,c=1}{\overset{M}{}}\underset{b,d=M+1}{\overset{N}{}}(\sigma _{ab},\sigma _{cd}^{}).$$
(3)
The variance of $`T`$, var($`T`$), is the statistical measure of a fundamental phenomenon in mesoscopic physics: For systems where quantum coherence is preserved the dimensionless conductance displays fluctuations of order unity irrespective of sample size, provided the dynamics is chaotic (or diffusive) and there are no tunneling barriers hindering the transmission. This phenomenon is known as “universal conductance fluctuations” (UCF) . Thus, a successful approximation scheme to explain UCF has to be accurate to the level of unity for the variance of $`T`$. In the specific case of quantum dots, i.e., ballistic electronic cavities, the random matrix theory  and the supersymmetric method  are, so far, the successful approaches to calculate var($`T`$).

The purpose of this work is twofold. First we analyze a very simple statistical measure – the average cross section – to show that the standard semiclassical $`S`$-matrix theory does not achieve the required precision to be useful as a theory for UCF. In doing this, we indicate its main sources of inaccuracy and discuss the main problems involved in improving the theory. We then show how to fix the inaccuracies by making explicit use of the unitarity of the $`S`$ matrix. This procedure is similar in spirit to those used in semiclassical studies of spectra of closed system . It can be viewed as a proposal for a set of semiclassical scattering sum rules to enforce well known exact symmetries of the $`S`$-matrix.

## II The semiclassical approach

We start with Miller’s semiclassical $`S`$-matrix formula  (including now transmission and reflections)

$$\stackrel{~}{S}_{ab}(E,X)=\underset{\mu (a,b)}{}\sqrt{p_\mu (E,X)}e^{i\varphi _\mu (E,X)/\mathrm{}},$$
(4)
where $`\mu (a,b)`$ labels the classical trajectories that start at channel $`b`$ and end at channel $`a`$, $`\varphi _\mu `$ are their reduced actions (with a Maslov phase included), and $`p_\mu `$ stands for the classical transition probability of going from $`a`$ to $`b`$ through the orbit $`\mu `$  (here and throughout the paper the tilde indicates that the semiclassical approximation is employed). It is implicit in the derivation of Eq. (4) that the number of open channels must be much larger than one and that there are no tunneling barriers between the leads and the cavity. When the scattering is chaotic (and the short time dynamics does not significantly contribute to $`S`$) the domains of applicability of the semiclassical theory and random matrix theory coincide and both approaches should be comparable. In this regime the semiclassical approach provides the dynamical explanation for the universality of the scattering fluctuations.

In general the semiclassical $`S`$-matrix is not exactly unitary at any given energy $`E`$. Indeed, it is only upon energy averaging and for the case of broken time-reversal symmetry (BTRS), that unitarity is automatically fulfilled. We now show this known result so as to present the basic elements and approximations employed in this paper. The energy averaged semiclassical cross section reads

$$\stackrel{~}{\sigma }_{ab}=|\stackrel{~}{S}_{ab}|^2=\underset{\mu ,\nu }{}\sqrt{p_\mu p_\nu }e^{i(\varphi _\mu \varphi _\nu )/\mathrm{}}.$$
(5)
Here $`\mathrm{}`$ indicates an energy average within an energy window where the classical dynamics presents little changes, nonetheless comprising many resonances. To compute the energy average one neglects the energy dependence of the probabilities $`p_\mu `$ and uses the diagonal approximation. The latter says that, on average, only orbits having the same action are correlated. If there are no symmetries present, this means that $`\mathrm{exp}[i(\varphi _\mu \varphi _\nu )/\mathrm{}]=\delta _{\mu \nu }`$. Then

$$\stackrel{~}{\sigma }_{ab}=\underset{\mu ,\nu }{}\sqrt{p_\mu p_\nu }\delta _{\mu \nu }=\underset{\mu }{}p_\mu .$$
(6)
The proof is completed by using the classical normalization condition

$$\underset{a=1}{\overset{N}{}}\underset{\mu (a,b)}{}p_\mu =1,$$
(7)
which insures that $`_a|\stackrel{~}{S}_{ab}|^2=1`$.

We shall assume that for any given entrance channel $`b`$, all exit channels $`a`$ are equivalent, i.e.,

$$\underset{\mu (a,b)}{}p_\mu =\frac{1}{N},$$
(8)
which yields

$$\stackrel{~}{\sigma }_{ab}=\frac{1}{N}.$$
(9)
The assumption of equivalent channels is justified (in the BTRS case) if the particle typically stays inside the interaction region time enough to be randomized, meaning that it becomes equiprobable to be ejected through any outgoing channel. The analysis of the other limiting case where time reversal symmetry is preserved will be postponed to Section III.

In order to clearly explain why unitarity problems affect the semiclassical theory of transmission fluctuations we introduce the object

$`\stackrel{~}{1}_a{\displaystyle \underset{b=1}{\overset{N}{}}}\stackrel{~}{\sigma }_{ab}={\displaystyle \underset{b=1}{\overset{N}{}}}{\displaystyle \underset{\genfrac{}{}{0pt}{}{\mu (a,b)}{\nu (a,b)}}{}}\sqrt{p_\mu p_\nu }e^{i(\varphi _\mu \varphi _\nu )/\mathrm{}}.`$ (10)
If the semiclassical $`S`$-matrix had been exact $`\stackrel{~}{1}_a=1`$; instead one has $`\stackrel{~}{1}_a=1`$. The lack of precision of the standard semiclassical scattering theory at the four-point level becomes evident by analyzing the variance $`(\stackrel{~}{1}_a,\stackrel{~}{1}_b)`$. The semiclassical approximation gives $`(\stackrel{~}{1}_a,\stackrel{~}{1}_b)0`$, leading to a “unit fluctuation” problem. To see this, using Eq. (4), we write

$$(\stackrel{~}{1}_a,\stackrel{~}{1}_b)=\underset{c,d=1}{\overset{N}{}}\underset{\genfrac{}{}{0pt}{}{\mu (a,c)}{\nu (a,c)}}{}\underset{\genfrac{}{}{0pt}{}{\mu ^{}(b,d)}{\nu ^{}(b,d)}}{}\sqrt{p_\mu p_\nu p_\mu ^{}p_\nu ^{}}\mathrm{exp}\left[\frac{i}{\mathrm{}}(\varphi _\mu \varphi _\nu +\varphi _\mu ^{}\varphi _\nu ^{})\right]1$$
(11)
so that the diagonal approximation yields

$$(\stackrel{~}{1}_a,\stackrel{~}{1}_b)=\underset{c,d=1}{\overset{N}{}}\underset{\genfrac{}{}{0pt}{}{\mu (a,c)}{\nu (a,c)}}{}\underset{\genfrac{}{}{0pt}{}{\mu ^{}(b,d)}{\nu ^{}(b,d)}}{}\sqrt{p_\mu p_\nu p_\mu ^{}p_\nu ^{}}(\delta _{\mu \nu }\delta _{\nu ^{}\mu ^{}}+\delta _{\mu \nu ^{}}\delta _{\nu \mu ^{}})1.$$
(12)
The first Kronecker $`\delta `$ product decouples the sums over orbits starting at channel $`c`$ and ending at $`a`$ from those entering the scattering region through channel $`d`$ and exiting through $`b`$. The resulting double sum adds up to unity. The second product contains crossed terms which vanish unless $`a=b`$ and $`c=d`$. Equation (12) becomes

$$(\stackrel{~}{1}_a,\stackrel{~}{1}_b)=\delta _{ab}\underset{c=1}{\overset{N}{}}\underset{\genfrac{}{}{0pt}{}{\mu (a,c)}{\nu (a,c)}}{}p_\mu p_\nu =\frac{\delta _{ab}}{N}.$$
(13)
This inaccuracy is neither unexpected, nor large. However, it has important consequences for the calculation of transmission fluctuations. This becomes evident by inspecting

$$(\underset{a=1}{\overset{N}{}}\stackrel{~}{1}_a,\underset{b=1}{\overset{N}{}}\stackrel{~}{1}_b)=(\underset{a,c=1}{\overset{N}{}}\stackrel{~}{\sigma }_{ac},\underset{b,d=1}{\overset{N}{}}\stackrel{~}{\sigma }_{bd})=10$$
(14)
which has the same double sum structure of the transmission variance and shows an inaccuracy exactly of the order of the effect that we aim to describe.

Let us be more explicit and go back to the analysis of the transmission autocorrelation function. Recalling Eq. (3) and assuming channels to be statistically equivalent we write

$$(T,T^{})=M^2(\sigma _{ab},\sigma _{ab}^{})+2M^2(M1)(\sigma _{ab},\sigma _{ac}^{})+M^2(M1)^2(\sigma _{ab},\sigma _{cd}^{}).$$
(15)
Here we use the convention that different indices $`a`$ and $`b`$ in the covariances imply that $`ab`$. This means that for the above equation $`bc`$ in the second term of its RHS, and $`ac`$ and $`bd`$ for the third one. We shall demonstrate below that, owing to unitarity, all three terms in the RHS of Eq. (15) are of the same order of magnitude. However, within the diagonal approximation, both the semiclassical covariances $`(\stackrel{~}{\sigma }_{ab},\stackrel{~}{\sigma }_{ac}^{})`$ and $`(\stackrel{~}{\sigma }_{ab},\stackrel{~}{\sigma }_{cd}^{})`$ are zero. Let us admit that the semiclassical approach gives the correct result for the transmission probability covariances to order $`1/N^2`$. Then, for a successful description of the transmission fluctuations, the theory has to be improved to access the first non vanishing order in the non diagonal terms $`(\sigma _{ab},\sigma _{ac}^{})`$ and $`(\sigma _{ab},\sigma _{cd}^{})`$, which are $`𝒪(N^3)`$ and $`𝒪(N^4)`$, respectively. Though desirable this is not really necessary. The alternative scheme we propose is to bypass the explicit semiclassical calculation of the nondiagonal covariances and use the unitarity of the $`S`$ matrix to relate the latter covariances to the diagonal one. Having expressed $`(T,T^{})`$ in terms of $`(\sigma _{ab},\sigma _{ab}^{})`$ alone, we use the semiclassical approximation only at the very end.

## III Enforcing unitarity

The relations among diagonal and nondiagonal covariances can be easily obtained from

$$(\underset{b=1}{\overset{N}{}}\sigma _{ab},\sigma _{cd}^{})=(1,\sigma _{cd}^{})=0,$$
(16)
which follows from unitarity. To proceed further we have to separately analyze the cases where either time reversal symmetry is absent (BTRS) or present (TRS). This distinction is necessary because the “elastic” processes ($`a=b`$) and the “inelastic” ones ($`ab`$) display different statistical properties when time reversal symmetry is preserved. Indeed it is well known that due to quantum interference, time reversal symmetry enhances the average reflection probability $`\sigma _{aa}`$ by a factor of two . This can be understood semiclassically by noting that in the TRS case there are pairs of orbits having the same action (time reversal partners) which contribute to $`\sigma _{aa}`$, thus interfering constructively to produce the factor two. Due to this effect the classical equivalence of channels breaks down at the quantum level. In this case the equivalence is only restored when time reversal symmetry is broken, leading to the considerations presented in Section II.

To illustrate the consequences of this phenomenon and the spirit of our scheme, let us analyze $`T(x)`$ in the crossover regime from TRS to BTRS. Recall that

$$T(x)=\underset{a=1}{\overset{M}{}}\underset{b=M+1}{\overset{N}{}}\sigma _{ab}(x)=M^2\sigma _{ab}(x).$$
(17)
Here $`x`$ parameterizes a Hamiltonian change breaking time reversal symmetry as $`x`$ grows from zero (TRS) to some critical value $`x^{}`$ (BTRS). Unitarity relates diagonal and off-diagonal averages:

$$1=\sigma _{aa}(x)+(N1)\sigma _{ab}(x).$$
(18)
This equation allows us to write $`T`$ in terms of $`\sigma _{aa}`$, the average that is semiclassically sensitive to time reversal effects, to obtain

$$T(x)=\frac{N^2}{4(N1)}(1\sigma _{aa}(x)).$$
(19)
For $`x=0`$ the elastic enhancement is maximal and hence $`T(x)`$ takes its smallest value. In mesoscopic physics, to distinguish from strong localization which is a phenomenon very different in origin, the reduction of transmission due to TRS is called the weak localization peak. Up to this point Eq. (19) is an exact expression. The semiclassical result is obtained by calculating $`\sigma _{aa}(x)`$ from Miller’s formula. For $`x`$ representing a magnetic field, the semiclassical approach gives a Lorentzian shape for the weak localization peak  in agreement with RMT . The amplitude of the weak localization correction can be readily obtained recalling that $`\stackrel{~}{\sigma }_{aa}(0)2/N`$ and $`\stackrel{~}{\sigma }_{aa}(xx^{})1/N`$, so that

$$\stackrel{~}{T}(0)\stackrel{~}{T}(x^{})=\frac{1}{4},$$
(20)
again in agreement with random matrix theory . The discussion above is not entirely original and was inspired by the pioneer semiclassical study of the weak localization peak in ballistic cavities developed by Baranger and collaborators . Based on the same strategy presented above, we are now ready to understand the UCF problem.

### A Transmission fluctuations in systems with broken time reversal symmetry

In this case all $`S`$ matrix elements are statistically equivalent. In order to express $`(T,T^{})`$ in terms of $`(\sigma _{ab},\sigma _{ab}^{})`$ it suffices to consider the following two independent unitarity equations

$$\underset{b=1}{\overset{N}{}}(\sigma _{ab},\sigma _{ac}^{})=0,\underset{b=1}{\overset{N}{}}(\sigma _{ab},\sigma _{cd}^{})=0$$
(21)
($`ca`$ in the second equation). The above relations can be reduced to:

$$(\sigma _{ab},\sigma _{ab}^{})+(N1)(\sigma _{ab},\sigma _{ac}^{})=0,(\sigma _{ab},\sigma _{ac}^{})+(N1)(\sigma _{ab},\sigma _{cd}^{})=0$$
(22)
(the convention about indices being the same as in Eq. (15)). Notice that these relations are not satisfied in the diagonal approximation. At the semiclassical level Eqs. (21) and (22) can be regarded as sum rules that go beyond the diagonal approximation. Insertion of Eqs. (22) into Eq. (15) readily renders

$$(T,T^{})=\frac{M^4}{(2M1)^2}(\sigma _{ab},\sigma _{ab}^{}).$$
(23)
As in the two-point analysis this equation is exact.

Now we are ready to employ the semiclassical approximation to compute $`(\sigma _{ab},\sigma _{ab}^{})`$. Let us first consider the case where $`x`$ stands for the energy, i.e.,

$$(\sigma _{ab},\sigma _{ab}^{})=C_{ab}(\epsilon )\sigma _{ab}(E+\frac{\epsilon }{2})\sigma _{ab}(E\frac{\epsilon }{2})_E\sigma _{ab}_E^2.$$
(24)
The semiclassical autocorrelation function $`\stackrel{~}{C}_{ab}(\epsilon )`$ can be calculated for classically small values of $`\epsilon `$, i.e., for energy differences such that the classical perturbation theory holds. In this case one keeps the stability coefficients constant and expands the actions to first order in $`\epsilon `$, i.e., $`\varphi _\mu (E\pm \epsilon /2)\varphi _\mu (E)\pm \tau _\mu \epsilon /2`$; here $`\tau _\mu `$ is the time the particle takes to travel from channel $`b`$ to channel $`a`$ along the orbit $`\mu `$. After the diagonal approximation we obtain

$`\stackrel{~}{\sigma }_{ab}(E+{\displaystyle \frac{\epsilon }{2}})\stackrel{~}{\sigma }_{ab}(E{\displaystyle \frac{\epsilon }{2}})={\displaystyle \underset{\genfrac{}{}{0pt}{}{\mu (a,b)}{\nu (a,b)}}{}}{\displaystyle \underset{\genfrac{}{}{0pt}{}{\mu ^{}(a,b)}{\nu ^{}(a,b)}}{}}`$ $`\sqrt{p_\mu p_\nu p_\mu ^{}p_\nu ^{}}(\delta _{\mu \nu }\delta _{\nu ^{}\mu ^{}}+\delta _{\mu \nu ^{}}\delta _{\nu \mu ^{}})`$ (26)
$`\times \mathrm{exp}\left[{\displaystyle \frac{i\epsilon }{2\mathrm{}}}\left(\tau _\mu \tau _\nu +\tau _\mu ^{}\tau _\nu ^{}\right)\right].`$
Using the same arguments employed after Eq. (12) we arrive at

$$\stackrel{~}{C}_{ab}(\epsilon )=\underset{\genfrac{}{}{0pt}{}{\mu (a,b)}{\nu (a,b)}}{}p_\mu p_\nu \mathrm{exp}\left[i\frac{\epsilon }{\mathrm{}}(\tau _\mu \tau _\nu )\right].$$
(27)
According to the analogue of the Hannay-Ozorio de Almeida sum rule for open systems ,

$$\underset{t\tau _\mu t+\delta t}{}p_\mu =\frac{\gamma }{N}e^{\gamma t}\delta t,$$
(28)
where $`_{t\tau _\mu t+\delta t}p_\mu `$ is the sum of all classical transition probabilities from channel $`a`$ to $`b`$ through trajectories within a small time interval $`[t,t+\delta t]`$, where $`\delta t`$ is classically small. The exponential is determined by the inverse escape time $`\gamma `$, later to be associated to an energy width $`\mathrm{\Gamma }=\mathrm{}\gamma `$. Replacing the sum over orbits by an integral over the time, we finally obtain

$$\stackrel{~}{C}_{ab}(\epsilon )=\frac{1}{N^2}\frac{1}{1+(\epsilon /\mathrm{\Gamma })^2}.$$
(29)
Before commenting on this result, we shall generalize it by accounting for an external parametric change $`X`$ in the Hamiltonian. For instance, in (mesoscopic physics) experiments $`X`$ is frequently an external magnetic field. The strategy to compute the generalized correlation function is, as above, based on classical perturbation theory. By expanding the reduced action to first order in $`X`$, we have to deal with $`Q_\mu \varphi _\mu /X`$. A full account of the technical details involved in calculating the parametric correlation can be found in Ref. . The basic step though is to compute the time average

$$e^{iQ_\mu \delta X/\mathrm{}}_{\delta t}=\mathrm{exp}\left[\frac{\delta X^2}{2\mathrm{}^2}Q^2(t)_{\delta t}\right].$$
(30)
Since $`Q^2(t)_{\delta t}`$ grows diffusively with time, i.e., $`Q^2(t)_{\delta t}=\alpha t`$, the autocorrelation function becomes

$$\stackrel{~}{C}_{ab}(\epsilon ,\delta X)=\frac{1}{N^2}\frac{1}{[1+(\delta X/X_c)^2]^2+(\epsilon /\mathrm{\Gamma })^2},$$
(31)
with

$$X_c^22\mathrm{}\mathrm{\Gamma }/\alpha .$$
(32)
Then the semiclassical result that includes unitarity restrictions is

$$(\stackrel{~}{T},\stackrel{~}{T}^{})=\frac{1}{16}\frac{1}{[1+(\delta X/X_c)^2]^2+(\epsilon /\mathrm{\Gamma })^2}+𝒪(1/N).$$
(33)
Remarkably, this result agrees exactly with the dimensionless conductance autocorrelation function for open ballistic dots in the limit $`N1`$ obtained by Efetov  using the supersymmetric technique. The agreement extends also to the structure of the parameter $`X_c`$ (32) if one relates $`\alpha `$ to the level velocity of closed systems as defined in Ref. . In this respect the semiclassical approach is complementary to random matrix theories, since it provides a dynamical interpretation for the nonuniversal quantities $`X_c`$ and $`\mathrm{\Gamma }`$.

### B Systems with time reversal symmetry

Now the $`S`$ matrix is symmetric and the statistical properties of diagonal and off-diagonal elements are different. Hence we need to write down two additional unitarity relations, as compared with the BTRS case, in order to single out the elastic case separately:

$$\underset{b=1}{\overset{N}{}}(\sigma _{ab},\sigma _{aa}^{})=0,\underset{b=1}{\overset{N}{}}(\sigma _{cb},\sigma _{aa}^{})=0,\underset{b=1}{\overset{N}{}}(\sigma _{ab},\sigma _{ac}^{})=0,\underset{b=1}{\overset{N}{}}(\sigma _{ab},\sigma _{cd}^{})=0$$
(34)
($`c,da`$). In terms of the basic covariances, the above system of equations is rewritten as

$`(\sigma _{aa},\sigma _{aa}^{})+(N1)(\sigma _{aa},\sigma _{ab}^{})`$ $`=`$ $`0`$ (35)
$`(\sigma _{aa},\sigma _{ab}^{})+(\sigma _{aa},\sigma _{bb}^{})+(N2)(\sigma _{aa},\sigma _{bc}^{})`$ $`=`$ $`0`$ (36)
$`(\sigma _{ab},\sigma _{ab}^{})+(\sigma _{aa},\sigma _{ab}^{})+(N2)(\sigma _{ab},\sigma _{ac}^{})`$ $`=`$ $`0`$ (37)
$`(\sigma _{aa},\sigma _{bc}^{})+2(\sigma _{ab},\sigma _{ac}^{})+(N3)(\sigma _{ab},\sigma _{cd}^{})`$ $`=`$ $`0,`$ (38)
where the channel index convention is that following Eq. (15). The only difference with the BTRS case is the factor 2 in the last equation, which is a consequence of the symmetry of $`S`$. As in the preceding subsection, we would like to express all covariances in terms of $`(\sigma _{aa},\sigma _{aa}^{})`$ and $`(\sigma _{ab},\sigma _{ab}^{})`$ which are the only nonzero ones in the diagonal approximation. Regrettably, we have more unknowns than equations, and it is not possible to obtain an exact equation like Eq. (23). However, as we are only interested in a relation which is correct to leading order in $`1/N`$, it suffices to consider the simplified system

$$(\sigma _{ab},\sigma _{ab}^{})+N(\sigma _{ab},\sigma _{ac}^{})=𝒪(N^3),2(\sigma _{ab},\sigma _{ac}^{})+N(\sigma _{ab},\sigma _{cd}^{})=𝒪(N^4),$$
(39)
which is obtained from the last two equations in (38) by keeping only the leading terms. These relations are the TRS analogues of (22) and lead to

$$(T,T^{})\frac{M^2}{2}(\sigma _{ab},\sigma _{ab}^{}).$$
(40)
Semiclassically, time reversal effects only manifest themselves in the diagonal covariances $`(\sigma _{aa},\sigma _{aa}^{})`$. The correlator $`(\stackrel{~}{\sigma }_{ab},\stackrel{~}{\sigma }_{ab}^{})`$ is the same as that for the BTRS case. Thus, at the semiclassical level, the effect of time reversal symmetry is to enhance the transmission fluctuations by a factor of two (cf. Eq. (23)), without changing the shape of the correlation function, that is

$$(\stackrel{~}{T},\stackrel{~}{T}^{})=\frac{1}{8}\frac{1}{[1+(\delta X/X_c)^2]^2+(\epsilon /\mathrm{\Gamma })^2}+𝒪(1/N).$$
(41)
We are not aware of any study of the transmission autocorrelation function for the TRS case using the supersymmetric method. For technical reasons it is much simpler to obtain the variance var$`(T)`$ using random matrix theory. This result is known  and, for $`N1`$, agrees with our semiclassical calculation

$$\text{var}(\stackrel{~}{T})=\frac{1}{8}.$$
(42)
## IV Concluding Remarks

Spectral studies in closed system have shown that the diagonal approximation should start to fail when the orbits involved have periods of the order of the Heisenberg time $`\tau _H`$. In scattering systems, the contribution of orbits with periods larger than the mean escape time $`\tau _e`$ is negligible. Given that in the semiclassical regime $`\tau _e\tau _H`$ it is generally accepted that the diagonal approximation should be unproblematic for scattering systems.

However, we have shown that the standard semiclassical approach fails to describe the transmission fluctuations because the diagonal approximation does not preserve the unitarity of the $`S`$ matrix to the required precision. One way to circumvent this problem, perhaps the most satisfactory from a theoretical point of view, is to improve the semiclassical theory to include correlations between different orbits. Alternatively, we have shown that the unitarity of the $`S`$ matrix can be used to express the transmission autocorrelation function in terms of transmission probabilities. Such expression contains some information about unitarity allowing the standard semiclassical approximation to be invoked resulting in a theory consistent with UCF.

Other difficulties are also encountered when calculating the transmission correlations: The semiclassical transmission correlator is not translationally invariant. For instance, this is manifest in the fact that

$$\stackrel{~}{T}(E)\stackrel{~}{T}(E+\epsilon )\stackrel{~}{T}(E+\epsilon /2)\stackrel{~}{T}(E\epsilon /2),$$
(43)
which can easily be checked by inspection. In our calculations we preferred to use $`\stackrel{~}{T}(E+\epsilon /2)\stackrel{~}{T}(E\epsilon /2)`$ because it is explicitly real. This choice is consistent with the spirit of this work, i.e., all information about exact quantum symmetries must be used in trying to compensate for the shortcomings of the semiclassical $`S`$ matrix.

###### Acknowledgements.

The authors gratefully acknowledge discussions with A. M. Ozorio de Almeida and O. Bohigas. This work was partially supported by CNPq and PRONEX (Brazil).


text:
# HST UV and Keck HIRES Spectra of BALQSOs

## 1. Introduction

BALs are present in about 10% of all optically selected quasars (Weymann et al. 1991). The absorption features result from mass outflows with velocity widths of order 2000 to 20 000 km s-1 and maximum velocities to 0.1$`c`$ and possibly higher in a few cases. The chemical abundances in the BAL regions are of interest as possible indicators of chemical enrichment in galactic nuclei (e.g. Korista et al. 1996, Hamann and Ferland 1999). The absorption features in BAL quasars are not easy to interpret because the BAL region may cover only a part of the background source(s) (Hamann 1998, Arav 1997). Partial covering along the line of sight is common in narrower intrinsic absorbers (e.g. Barlow, Hamann, and Sargent 1997), but more difficult to determine in BAL quasars where the strong doublets of Si IV and C IV are typically blended into wide features. In narrower intrinsic absorption systems, the partial covering is both ion and velocity dependent (Barlow and Sargent 1997). Partial covering definitely influences some narrow BAL components as determined from HIRES observations of CSO 755 (Barlow and Junkkarinen 1994) and Q0226$``$1024.

In this conference proceedings paper, we report on a program that uses Keck HIRES spectra in the analysis of the BALs. BAL features in the UV (observed frame) are analyzed using lower resolution spectra obtained from the HST archive. The HIRES spectra contribute in a number of areas to the analysis. Here we report on: 1.) BAL smoothness, and 2.) absorption templates. As a by–product of the template generation, the the HIRES spectra provide some information on partial covering.

## 2. Smoothness of BAL Features

The observed smoothness of the BAL features in HIRES spectra rules out a “picket fence” model for the BALs. A “picket fence” model (partial covering by turbulent components in velocity space) was proposed by Kwan (1990) in order to explain the relative weakness of the H I Ly $`\alpha `$ BAL without resorting to non–solar chemical abundances or partial covering along the line of sight. The smooth BAL features also imply a large number of “clouds” in the BAL region if the BAL region is composed of clouds rather than a smooth outflow.

In order to quantify the smoothness of the BAL features, the C IV BAL in Q1246$``$047 has been divided by a piecewise polynomial. A small number of polynomials of low order were used to preserve residual fluctuations on scales less than $``$ 200 km s-1. The result of that division is shown in Figure 1.

The entire C IV BAL feature spans absorption velocities from 10 000 km s-1 to 27 000 km s-1.

In the C IV BAL, from 4700 Å to 4760 Å (chosen because the optical depth is roughly constant), there are 375 8.8 km s-1 bins. Each bin is four pixels, about the FWHM resolution for this HIRES spectrum. If we ignore the fact that the bins are not completely independent and and also ignore the doublet nature of the C IV transition, an estimate of the number of independent “clouds” can be made from the noise in the divided C IV spectrum. The residual intensity is assumed to be given by $`r`$ = $`e^\tau `$ with $`\tau `$ = $`N\tau _c`$ where $`N`$ is the number of clouds contributing to the absorption in each bin and $`\tau _c`$ is the optical depth per cloud. If the clouds obey a simple gaussian distribution with its $`N^{1/2}`$ rms variation in number, then the rms fluctuations in the divided spectrum, $`\sigma ^2`$ = $`<(\delta r/r_s)^2>`$, will be given by: $`\sigma \tau \delta N/N`$ = $`\tau N^{1/2}`$. Here $`\delta r=rr_s`$ and $`r_s`$ is the smooth fit to the data. Putting in the observed $`\sigma =0.059`$ and $`\tau 1`$ in this wavelength range, gives N $``$ 300 clouds and multiplying by 375 bins gives $`N_{total}10^5`$ clouds. This is a very crude estimate, but it is clear that a large number of clouds are needed to make a smooth trough. The residuals observed are at a level slightly higher than expected from the noise estimate in the spectrum ($`\chi _{\nu }^{}{}_{}{}^{2}=1.8`$, while 1.0 is expected if purely from noise). Given the process of piecing together the HIRES spectral orders, fitting a continuum, and then fitting the trough with a piecewise polynomial, it is possible that all of the observed variation is noise plus some fitting errors.

This analysis is most sensitive to a large number of clouds at the resolution of the observation. Above a few hundred km s-1, for the C IV trough in Q1246-057, some structure is removed by the polynomial fit used to model the smooth trough. The bin size can easily be varied and repeating this exercise shows that for “cloud” (or component) widths from 5 to 200 km s-1 a large number ($`3\times 10^4`$) of clouds is needed. The assignment of a typical velocity width for a typical cloud is uncertain because the physical mechanism behind BAL cloud confinement is not known. Photoionization at parsec distances or greater leads to a much larger number of very small individual clouds and small filling factors (e.g. Junkkarinen, Burbidge, and Smith 1987). Velocity widths $``$ 8 km s-1 (FWHM) are produced by thermal broadening for carbon at T $``$ 15 000 K, near the temperature expected from photoionization equilibrium.

The smoothness of the troughs in BAL quasars like Q1246$``$057 may instead indicate a smooth outflow. Models that avoid the need for small clouds have been calculated by Murray et al. (1995). In these models the emission and absorption regions are both formed very close to the central engine (starting point as near as $``$0.003 pc), and the absorption is produced by a smooth outflow that crosses the line of sight at an angle.

## 3. Generation of Absorption Templates

The conventional analysis of BAL spectra involves the extraction of absorption templates from the data. Doublets like C IV $`\lambda \lambda `$ 1548.2,1550.8 and Si IV $`\lambda \lambda `$ 1393.8,1402.8, can be iteratively corrected for the weaker line (Junkkarinen, Burbidge, and Smith 1983) to produce optical depth versus velocity. These templates are shifted to the wavelengths of other transitions and scaled in a $`\chi ^2`$ fitting procedure to match the data and give approximate (lower limit) column densities (e.g. Korista et al. 1992). Because BAL quasars like Q0226$``$1024 (Fig. 2) and Q1246$``$057 have smooth troughs

with no apparent features at scales around 30 km s-1, spectra obtained at the HIRES resolution (typically 7 - 9 km s-1 FWHM) can be smoothed to produce high quality templates.

Figure 3 shows the C IV and Si IV absorption templates extracted from

our Keck HIRES spectrum of Q0226$``$1024. The spectra were smoothed to produce these templates and could be further smoothed without losing any of the apparent structure. At the HIRES resolution of 7 km s-1 FWHM for Q0226$``$1024 and at a resolution of 9 km s-1 FWHM for Q1246$``$057 the troughs are completely resolved. The troughs are not without structure as is illustrated in the case of Q0226$``$1024. The lowest velocity BAL feature (marked “1” in Figs. 2 & 3) breaks up into three “spikes” of absorption repeated in both C IV and Si IV. These features are not resolved with $`R1000`$ spectra.

Analyzing BAL quasar spectra using multiple templates that cover only a part of the velocity space may be possible when the BALs occur in clumps well separated in velocity. Troughs 1 and 2 in Q0226$``$1024 are narrower than the Si IV $`\lambda \lambda `$ 1393.8,1402.8 doublet. Trough 2 shows partial covering in Si IV with $`C_f0.70`$ based on measurements of the doublet using: $`C_f=\frac{I_{1}^{}{}_{}{}^{2}2I_1+1}{I_22I_1+1}`$, where $`I_1`$ and $`I_2`$ are the residual intensities in the stronger and weaker lines in the doublet (e.g. Hamann et al. 1997). The template extraction procedure assumes full covering and produces a false absorption feature around 7500 km s-1 in the extracted template (marked “art.”Fig. 3). Such weak, echo–like features and regions where the template goes negative are indications that the assumption of complete coverage of the background source has broken down. Artifacts can also be produced by a poor choice of continuum, so the templates must be evaluated allowing for some uncertainty in the continuum. For very wide features with smooth edges compared to the doublet separation, like trough 3 in C IV in Q0226$``$1024, it is easy to construct partial covering models that mimic the data. The data are consistent with either 100% covering over those velocities or with high optical depths and a covering function that is chosen to produce the shape of the observed feature. The important issue of partial covering dominating the shape of the broad BAL troughs is not one that is easily resolved.

## 4. Summary

The BALs in Q1246$``$057 and Q0226$``$1024 are found to be smooth and completely resolved in the Keck HIRES spectra at a resolution of 7 – 9 km s-1 FWHM. The smoothness of the C IV trough in Q1246$``$057 leads to an estimate of at least $`3\times 10^4`$ clouds (or components) of width 5 to 200 km s-1 comprising the deepest part of the trough. Keck HIRES spectra are a good source for generating absorption templates for analyzing lower resolution ground based and HST UV spectra of BAL quasars. The spectrum of Q0226$``$1024 shows BAL features with structure that is not resolved in low resolution spectra. The Q0226$``$1024 Si IV template also shows artifacts produced by a breakdown of the assumption of complete covering of the background source. In broader BAL features (broad relative to the doublet separation), the effects of optical depth and partial covering are not easy to separate. Spectropolarimetry (e.g. Cohen et al. 1997) or photoionization equilibrium analysis could yield estimates of the partial covering and the true column densities in the broad features.

### Acknowledgments.

This work has been supported by an archival research grant (AR-08355.01-97A) from the Space Telescope Science Institute which is operated by AURA, Inc., under NASA contract NAS 5-26555.

## References

Arav, N. 1997 in Mass Ejection from AGN eds R. Weymann, I. Shlosman, and N. Arav, ASP Conf. Series, 208

Barlow, T. A., and Sargent, W. L. W. 1997, AJ, 113, 136

Barlow, T. A., and Junkkarinen, V. T. 1994, BAAS, 26, 1339

Barlow, T. A., Hamann, F., and Sargent, W. L. W. 1997 in Mass Ejection from AGN eds R. Weymann, I. Shlosman, and N. Arav, ASP Conf. Series, 13

Boksenberg, A., Carswell, R. F., Smith, M. G., and Whelan, J. A. J. 1978, MNRAS, 184, 773

Cohen, M. H., Ogle, P. M., Tran, H. D., Vermeulen, R. C., Miller, J. S., Goodrich, R. W., and Martel, A. R. 1997, ApJ, 448, L77

Hamann, F. 1997, ApJS, 109, 279

Hamann, F. 1998, ApJ, 500, 798

Hamann, F., Barlow, T. A., Cohen, R. D., Junkkarinen, V., and Burbidge, E. M. 1997 in Mass Ejection from AGN eds R. Weymann, I. Shlosman, and N. Arav, ASP Conf. Series, 19

Hamann, F., and Ferland, G. J. 1999, ARAA, 37, 487

Junkkarinen, V. T., Burbidge, E. M., and Smith, H. E. 1983, ApJ, 265, 51

Junkkarinen, V. T., Burbidge, E. M., and Smith, H. E. 1987, ApJ, 317, 460

Korista, K., Hamann, F., Ferguson, J., and Ferland, G. 1996, ApJ, 461, 641

Korista et al. 1992, ApJ, 401, 529

Kwan, J. 1990, ApJ, 353, 123

Murray, N., Chiang, J., Grossman, S. A., and Voit, G. M. 1995, ApJ, 451, 498

Weymann, R.J., Morris, S.L., Foltz, C.B., and Hewett, P.C. 1991, ApJ, 373, 23

Young, P., Sargent, W. L. W., and Boksenberg, A. 1982, ApJS, 48, 455


text:
# Density functional study of the adsorption of K on the Cu(111) surface

## I Introduction

The study of adsorbates on metal surfaces is of high importance for scientists as well as for industry with potential applications, for example in catalysis. Alkali metals are relatively simple systems to consider as adsorbates. Initially, it was assumed that they would always occupy high-coordination sites. It was therefore a big surprise when a first system was discovered where Cs, adsorbed on the Cu(111) surface, occupied the top site and not the threefold hollow site . Meanwhile, further systems of alkali metals with top adsorption have been found — typically heavier alkali atoms (from K on) on closed packed surfaces (for a review, see references ). The situation is thus more complex than in the case of halogens where the adsorption site on closed-packed surfaces is usually the threefold hollow site.

Due to the increase in computational power, the theoretical study with methods based on density functional theory (DFT) of these adsorbate systems has become feasible in the last few years. For example, systems such as Na and K on the Al(111) surface or Na on the Cu(111) surface  have been studied recently.

In this article, we study the adsorption of potassium on the Cu(111) surface as a model system for alkali adsorption on metal surfaces. This is an extension of earlier work of halogens on metallic surfaces (Cl on Cu(111)  and Cl on Ag(111) ). For the system Cu(111) (2$`\times `$2)-K, adsorption on the top site was observed experimentally . The addressed questions are therefore whether first principles simulation is able to reproduce the preferred adsorption site, the magnitude of the energy splitting of different highly symmetric adsorption sites, the geometry, the charge of the adsorbate, and the mechanism of the bond.

The applied methods are all-electron full-potential calculations with a local Gaussian basis set. Mainly gradient corrected density functional calculations were performed, the energetically most favorable structure was additionally optimized with the local density approximation, for comparison.

## II Computational Parameters

A local basis set formalism was used where the basis functions are Gaussian type orbitals centered at the atoms as implemented in the code CRYSTAL . For Cu, a $`[6s5p2d]`$ all-electron basis set as used in previous studies on copper metal and chlorine adsorption on copper metal was employed . The K all-electron basis set from work on alkali halides was chosen , with the two outermost $`sp`$-exponents replaced by two $`sp`$-exponents optimized for the free K atom (0.29 and 0.08 a.u.) and an additional $`d`$-exponent (0.50 a.u.), resulting in a $`[5s4p1d]`$ basis set. Compared to the calculations on alkali halides, more diffuse basis functions are necessary because the potassium atom is not fully ionized and a description of its $`4s`$ and $`4p`$ states is required. A further enlargement of the potassium basis set is achieved indirectly because basis functions from neighboring centers are used to describe the charge distribution.  The bulk of the calculations was done with the gradient corrected exchange and correlation functional of Perdew and Wang (GGA) . For the energetically most favorable site, the geometry was re-optimized at the level of the local density approximation (LDA) with Dirac-Slater exchange  and the Perdew-Zunger correlation functional , for comparison.

An auxiliary basis set was used to fit the exchange-correlation potential. For copper, it consisted of 12 even tempered (i.e. the ratio from one to the next higher exponent was kept fixed) $`s`$-exponents and 12 $`p`$-exponents in the range from 0.1 to 2000, 8 $`d`$-exponents and 8 $`f`$-exponents in the range from 0.1 to 100. For potassium, the same $`s`$\- and $`p`$-exponents were chosen, and 5 $`d`$-exponents in the range from 0.8 to 100.

The adsorption was modeled by using a three-layer copper slab with the copper atoms arranged as in the face-centered cubic (fcc) lattice, at the GGA-optimized bulk Cu lattice constant of 3.63 Å. Potassium was adsorbed on one side of this slab. This is presently the computational limit for desktop workstations with this approach. This is similar to earlier studies  where three layers of metal and a single-sided adsorbate layer were found to be sufficient for a theoretical description. A supercell approach with a (2$`\times `$2) adsorption pattern as in the experiment was used . This slab was not repeated in the third dimension so that the model is truly two-dimensional. The copper atoms in the top layer were allowed to relax vertically, an additional horizontal shift as observed in the adsorption of K on Ni(111)  would, however, require too much numerical effort to be simulated. For comparison, the vertical relaxation of the copper atoms was simulated in two different ways: simulations were performed where only a uniform relaxation of the top copper layer was possible, and simulations where a different vertical relaxation for the copper atoms in the top layer was possible (i.e. substrate rumpling).

Four adsorption sites were considered (see figure 1): the top adsorption site with K sitting vertically above a copper atom in the top layer, the bridge site with K sitting above the middle of two copper atoms in the top layer, and two different threefold hollow sites where the potassium atoms are placed vertically above a copper atom in the second (third) copper layer. These threefold hollow sites can not be distinguished when only the adsorbate and the positions of the atoms in the top copper layer are given, but instead the position of the atoms in the second and third layer under the adsorbate layer must be considered. The first of the threefold hollow sites is referred to as the hcp (hexagonal close-packed) hollow site because the potassium atom is vertically above a copper atom in the second copper layer. The second of the threefold hollow sites is referred to as fcc hollow site because the potassium atom is vertically above third layer copper atoms. In the following, we will use the notion hcp (fcc) hollow site to distinguish between these two adsorption sites. This is closely connected to the notion of hcp (versus fcc) lattices where there are atoms two (versus three) layers vertically below atoms in a certain layer of a solid.

With a Pack-Monkhorst net of shrinking factor 16, the number of points in the reciprocal lattice was 30 for the fcc hollow site and the hcp hollow site, and 73 for the bridge and top site. The Fermi function was smeared with a temperature of 0.01 $`E_h`$ (1$`E_h`$=27.2114 eV) to make the integration numerically more stable. For an extensive test of the various computational parameters for metallic systems with a local basis set technique, see reference .

## III Summary of previous experimental and theoretical Results

The adsorption of K on Cu(111) has been studied with surface-extended X-ray absorption fine-structure (SEXAFS) measurements . At a nominal coverage of 0.25$`\pm `$ 0.01 monolayer, a (2$`\times `$2) pattern was observed. The adsorption site was identified as the top site and a bond-length from K to the nearest Cu atom of 3.05$`\pm `$0.02 Å was deduced.

Cluster models  with Cu7 as the adsorbate gave in Hartree-Fock and density functional calculations the top site as the preferential one. However, the energy splitting was found to be relatively large (e.g. $``$ 0.5 eV at the DFT level), the computed bond length was in good agreement with the experimentally observed. The computed K charge was relatively large with 0.7 - 0.8 $`|e|`$ at the DFT level. Similar results for the energy splitting and bond length were then found when potentials were fitted to model the interaction of the adsorbate with the infinite surface.

GGA calculations have been performed for the systems Cu(111) (2$`\times `$2)-Na and Cu(111) (3/2$`\times `$3/2)-Na. It was found that hollow sites were preferred. Substrate rumpling was found to be strongest for the top site; in general copper atoms below sodium atoms moved into the substrate, whereas copper atoms without sodium in the vicinity moved outwards. The top site was the one which gained most energy from rumpling and thus the energy difference between the different adsorption sites was reduced.

The adsorption of sodium and potassium on the Al(111) surface has been studied theoretically with the LDA  and it was found that, whereas sodium adsorbed on a substitutional site, the fcc hollow site and the top adsorption site were degenerate for potassium for both structures considered ($`\sqrt{3}\times \sqrt{3}R30^{}`$ and 2$`\times `$2). Again, rumpling was most important for the top site.

## IV Results for K adsorption

In this section, the results of the calculations on the system Cu(111) (2$`\times `$2)-K are presented and discussed. Firstly, in tables I and II, the adsorption geometry and energy are displayed. We notice that the adsorption at the top site is energetically most favorable, i.e. the experimental situation is reproduced. For this site, the computed adsorption energy per potassium atom is 47 $`mE_h`$ (1.28 eV). However, the other considered sites are only slightly higher in energy (by less than 1 $`mE_h`$). This is close to the limit of what can be resolved and there are still parameters which might have an influence on the prediction of the adsorption site (e.g. numbers of layers in the slab model, a possible horizontal relaxation of the copper atoms, basis set deficiencies due to the lack of availability of $`f`$-functions). The magnitude of the energy splitting is thus much lower as previously found for halogens , but in good agreement with findings for Na on Cu(111)  and Na or K on Al(111) .

The value for the adsorption energy is in the range of that for potassium on graphite (0.48 to 0.89 eV, depending on the coverage and the relaxation), or that for Na on Cu(111) which was computed to be 1.8 to 1.9 eV .

The binding energy of a free K layer (with a K-K nearest neighbor distance as in the adsorbate system, 5.13 Å) was computed for comparison and a value of 0.0229 $`E_h`$, i.e. 0.62 eV was obtained. This is in reasonable agreement with previous calculations (0.56 eV , LDA, K-K nearest neighbor distance 4.94 Å; or 0.83 eV , LDA, K-K nearest neighbor distance 4.52 Å; in the latter work the energy of the free atom was obtained from a calculation without spin-polarization).

We notice that the K-Cu bond length increases from 2.83 Å (top site) $`<`$ 3.04 Å (bridge site) $`<`$ 3.11 Å (fcc, hcp hollow site). This is in agreement with the argument that the bond should be the stronger and the bond length therefore the shorter, the lower the number of copper neighbors . It is consistent with results from simulations for halogens on metal surfaces . In addition, we note that those atoms in the Cu surface, which are closest to the K atom, relax inwards. This relaxation is strongest for the structure with the lowest number of nearest neighbors underneath the K atom — in full agreement with the findings in the case of Na on Cu(111) . The order of magnitude (0.165 Å inwards relaxation of copper atom 1 under the potassium atom, relative to atoms 2,3,4) is in line with Na on Cu(111) (0.1 Å) and with one experiment for K on Ni (111) (0.12 Å) , less with the other experiment for K on Ni(111) (0.01 $`\pm `$ 0.09 Å) .

The computed bond length is shorter than measured in the experiment (3.05 $`\pm `$ 0.02 Å). To estimate the errors due to the choice of the functional, calculations with the LDA were performed for the top site, for comparison. The LDA bond length (2.73 Å) is slightly shorter as the GGA bond length. If we assume a copper radius of 3.63/2$`\sqrt{2}`$ Å, we obtain an effective radius, at the GGA level, of 1.55 Å which is in the range of the experimentally observed value for top adsorption of potassium (1.77 Å for K on Cu(111), 1.57 … 1.77 Å for K on Ni(111)) — see reference  and references therein.

In addition, calculations for the same adsorption sites were performed when rumpling was not allowed, but instead only a uniform relaxation of the copper atoms in the top Cu layer (table II). In these simulations, the fcc hollow site was found to be lowest in energy, with the hcp hollow site and the bridge site of the order of $``$ 0.2 $`mE_h`$ higher in energy, i.e. nearly degenerate. The top site was highest in energy, but only by less than $`1mE_h`$, however. The bond lengths are relatively similar to the case where rumpling was allowed, the atoms in the top Cu layer relaxed inwards by $``$ 0.03 Å. We can thus conclude that rumpling is crucial to obtain the top site as the preferred site — the top site gains $`>2`$ $`mE_h`$ due to rumpling, whereas all the other sites gain less than 1 $`mE_h`$.

In table III, Mulliken charges for the potassium atom are given, projected on the different basis functions. The free atom in its $`{}_{}{}^{2}S`$ state has 7 $`s`$ and 12 $`p`$ electrons, obviously $`p_x`$, $`p_y`$ and $`p_z`$ are degenerate. In the free and neutral K layer, $`p_x`$, $`p_y`$ and $`p_z`$ population slightly increase whereas the $`s`$ population decreases. Finally, in the adsorbate systems, $`p_x`$, $`p_y`$ and $`p_z`$ charges are slightly above 4, the number of $`s`$-electrons is $``$ 6.5, and the total charge is $``$ +0.1 $`|e|`$. Charges in $`p_x`$ and $`p_y`$ orbitals are identical except for the bridge site - as in the case of Cl on Ag(111), the $`p_x`$ orbital which has more overlap with the substrate layer (in our choice of geometry — figure 1) is slightly less occupied than the $`p_y`$ orbital. However, the difference is much smaller than in the case of Cl on Ag(111), and it is hardly visible in the density of states (DOS) — see the discussion in the following paragraph. In addition, the overlap population is very small: for K and next neighbor Cu, it is 0.06 $`|e|`$, and it rapidly decreases for the copper atoms further apart. All this indicates that there is no evidence for hybridisation and covalent bonding.

In figure 2, the DOS, projected on the potassium basis functions, is displayed for the top adsorption site. The Fermi energy is in a regime with a relatively large contribution from K 4$`s`$ and 4$`p`$ bands, so that the overlayer is clearly metallic. It is interesting that the projected DOS does not depend on the adsorption site: it looks virtually identical for top, hcp hollow, fcc hollow and bridge site. This is different from the case of chlorine as an adsorbate, where the projected DOS clearly depended on the adsorption site. Another feature which was found for the bridge site in the chlorine adsorption was the different projected DOS for $`p_x`$ and $`p_y`$ orbitals: however, this is hardly visible for potassium and the DOS for $`p_x`$ and $`p_y`$ is virtually identical.

Also, the values of the K $`3s`$ level (-1.19 $`E_h`$ with respect to the Fermi level) and $`3p`$ levels (-0.59 $`E_h`$ with respect to the Fermi level) are practically independent of the adsorption site. This is again in contrast to chlorine: for chlorine, the core eigenvalue depended on the adsorption site, and it was correlated with the charge of the chlorine atom . For K, the variation of the Mulliken charges with adsorption site is much smaller (table III) as for chlorine. This is consistent with the finding that the core eigenvalue does not vary for the different sites. The Mulliken charge for K at the top site is $``$ +0.12, i.e. K is slightly positive charged. This is in reasonable agreement with the findings for K on graphite, where, depending on the coverage and the relaxation, charges in the range from 0.17 to 0.38 $`|e|`$, were obtained .

## V Summary

In this article, all-electron full-potential density functional calculations were applied to compute properties of the system Cu(111) (2$`\times `$2)- K. The top site was found as the preferable adsorption site, with the other considered sites being nearly degenerate. Substrate rumpling was crucial to obtain this result. The bond length was computed to be 2.83 Å, the binding energy 1.28 eV. The potassium charge was computed to be +0.1 $`|e|`$. Charge and projected density of states varied only very little for the different adsorption sites, and similarly the position of the K $`3s`$ and $`3p`$ core eigenvalues did not vary. No evidence for a covalent contribution to the binding was found, so that the mechanism should rather be a metallic bond.