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# Mixed state properties of superconducting MgB2 single crystals

## Abstract

We report on measurements of the magnetic moment in superconducting MgB2 single crystals. We find $`\mu _0H_{c2}^c(0)`$ = 3.2 T, $`\mu _0H_{c2}^{ab}(0)`$ = 14.5 T, $`\gamma `$ = 4.6, $`\mu _0H_c(0)`$ = 0.28 T, and $`\kappa (T_c)`$ = 4.7. The standard Ginzburg-Landau and London model relations lead to a consistent data set and indicate that MgB2 is a clean limit superconductor of intermediate coupling strength with very pronounced anisotropy effects.

The recent discovery of superconductivity in MgB2 Nag01  has attracted a lot of attention. Especially the rather high transition temperature of nearly 40 K in such a simple compound is of interest for applications, but also for an analysis of the physical mechanism leading to superconductivity. Several experiments indicate a phonon mediated s - wave BCS mechanism Bud01 ; Qui02 . Different models are proposed to explain the particular properties of MgB2 Haa01 ; Shu01 . Their correctness has to be checked by experiments, but only a few results are available on single crystals Lee01 ; Pra01 ; Elt02 ; Man02 ; Ang01 ; Sol01 ; Wel02 .

We report in this Letter on magnetization measurements on single crystalline MgB2 in magnetic fields applied parallel and perpendicular to the uniaxial crystallographic ($``$ c) axis. A detailed evaluation allows us to obtain the temperature dependence of the most important reversible mixed state parameters, such as the critical magnetic fields, the characteristic lengths, the Ginzburg-Landau (GL) parameter and the anisotropy. We will show that MgB2 is a clean limit superconductor of intermediate coupling strength with very pronounced anisotropy effects.

Several single crystals of MgB2 were grown using high pressure cubic anvils. Details of the process will be published elsewhere Kar02 . Two crystals (sample A: $`a\times b\times c660\times 570\times 21\mu m^3`$; sample B: $`a\times b\times c600\times 384\times 54\mu m^3`$) were investigated by magnetic methods. The transition temperature ($`T_c`$) of each sample was obtained from the ac - susceptibility measured in a 1 T quantum interference device (SQUID) magnetometer. Sample A shows an onset of $`T_c`$ at 38 K and a rather broad transition of about 1 K. A linear fit of $`H_{c2}^c`$ vs. $`T`$ near $`T_c`$ indicates a ”bulk transition temperature” of 37.5 K (see inset of fig. 1a). In sample B we find $`T_c`$ = 38.3 K, $`\mathrm{\Delta }T_c`$ = 0.3 K and a ”bulk $`T_c`$” of 38.2 K. A simple analysis Ang91  of the slope of the magnetic moment after reversing the applied field demonstrates that the size of the domain, in which the supercurrents flow without impedance, is identical to the sample size. Furthermore, a comparison of the calculated and the measured magnetization in the Meissner regime indicates a superconducting volume fraction of about 100 %. The further evaluation of the mixed state parameters did not show significant differences between these two crystals.

The measurements of the magnetic moment were carried out in the 1 T and in an 8 T (SHE) SQUID magnetometer (for details, cf. Sau98 ). Fig. 1a shows the upper critical field of MgB2 for applied fields $`H_ac`$ ($`H_{c2}^c`$) and $`H_aab`$ ($`H_{c2}^{ab}`$). $`H_{c2}(T)`$ is determined either from the onset of the superconducting signal in the $`m(T)`$ curve (”$`T_c(H_a)`$”) or from the disappearance of the superconducting signal in the $`m(H_a)`$ curve. The same results were obtained by both methods. $`H_{c2}^{ab}`$ could be evaluated directly only below 8 T ($`T>`$ 21 K in this case). At lower temperatures the London theory for the reversible magnetic moment $`m_r`$, i.e. $`m_r\mathrm{ln}(H_{c2}/H_a)`$, was used for the sake of simplicity to extrapolate the experimental $`m_r`$ data to zero. The very small magnetic moment in higher fields and the logarithmic behavior lead to rather large uncertainties in the evaluation, which are indicated by error bars in fig. 1a.

To obtain $`H_{c2}^c(0)`$, the data were fitted to the function $`H_{c2}(t)=H_{c2}(0)(1t^\alpha )^\beta `$ with $`\mu _0H_{c2}^c(0)`$ = 3.18 T ($`t=T/T_c`$, $`T_c`$ denotes the bulk transition temperature; $`\alpha `$, $`\beta `$ and $`H_{c2}(0)`$ are fit parameters). The initial slope of the upper critical field ($`k=\mu _0[H_{c2}/T]_{T_c})`$ is found to be -0.112 T/K near $`T_c`$, thus $`\mu _0H_{c2}^c(0)/(kT_c`$) = -0.75. This is close to the weak coupling BCS result ($``$ -0.73 in the clean limit, -0.69 would correspond to the dirty limit Hel66 ). $`H_{c2}(T)`$ is not very sensitive to the coupling strength and the above result, -0.75, is actually close to that of the strong coupling superconductor Pb Car90 , of course without considering anisotropy effects Haa01 ; Pit92 . If we apply the same procedure to $`H_aab`$, we obtain $`\mu _0H_{c2}^{ab}(0)`$ = 15 T. However, the slope was determined in this case from the linear region above 1 T ($`k`$ = -0.55 T/K) and the corresponding extrapolated ”$`T_c`$” of 36.1 K, because a strong positive curvature of $`H_{c2}^{ab}(T)`$ is observed in the vicinity of $`T_c`$ (cf. the inset of fig. 1a), which represents a well known feature of anisotropic superconductors, e.g. of the high $`T_c^{}s`$, but also of conventional superconductors, such as Nb. The Fermi surface and the electron phonon coupling are usually held responsible for these anisotropic properties. According to Pit92 , the high temperature end of $`H_{c2}^{ab}(T)`$ can be obtained by an anisotropic Fermi surface, but not by the coupling alone. In Nb, e.g., $`H_{c2}(T)`$ is well explained by an anisotropic Fermi velocity and an anisotropic electron phonon coupling Web91 . A similar model could possibly apply in the case of MgB2, but alternative theories (e.g. a two band model Shu01 ) are also under discussion.

The upper critical field anisotropy $`\gamma =H_{c2}^{ab}/H_{c2}^c`$ is shown in Fig. 1b (full squares). It increases from about 1 near $`T_c`$ to 4.2 at 22 K, in qualitative agreement with previous results Ang01 ; Sol01 ; Wel02 . The open squares refer to results from torque measurements taken in a 9 T (Quantum Design) PPMS system. In this case, the angular dependence of the reversible torque is fitted to the anisotropic London theory with three fit parameters $`\gamma `$, $`H_{c2}^c`$ and $`\lambda _{ab}`$ (cf. Zec96 ). A comparison of the latter two parameters with results from the SQUID measurements shows the high reliability of the evaluation. Note that this method does not lead to the anisotropy of the upper critical field, but rather to that of the magnetic penetration depth ($`\lambda `$), which can, in general, deviate from $`H_{c2}^{ab}/H_{c2}^c`$. In MgB2, both seem to be the same, at least for $`T`$ 30 K. The torque indicates a small increase of $`\gamma `$ from 4.3 at 20 K to about 4.5 at 5 K leading to $`\gamma (0)4.55`$. However, we cannot exclude some small systematic errors in the evaluation, because (i) most of the recorded torque data refer to the irreversible regime. Therefore, the reversible signal ($`\tau `$) has to be calculated from the irreversible branches at increasing ($`\tau _+`$) and decreasing ($`\tau _{}`$) angles ($`\tau =[\tau _++\tau _{}]/2`$). The difference between the two branches is rather small, but grows at lower temperatures. (ii) The angular dependence of the background signal varies with temperature and cannot be determined exactly from measurements without a sample. However, different data sets for the background do not change $`\gamma `$ at 5 K significantly. Furthermore, the torque data were evaluated at several magnetic fields (0.5 - 2 T), the differences in $`\gamma `$ were very small (2 %). Based on the excellent agreement between the SQUID and the torque data in the overlapping temperature range, we assume that $`\lambda _c/\lambda _{ab}=H_{c2}^{ab}/H_{c2}^c`$ for $`T<`$ 21 K, which allows us to calculate $`H_{c2}^{ab}`$ in this temperature range (cf. the solid squares for $`H_{c2}^{ab}`$ at $`T<`$ 21 K in fig. 1a). This leads to $`H_{c2}^{ab}`$(0) = 14.5 T.

The further mixed state parameters can be calculated from the London theory and some Ginzburg-Landau relations. For instance, the magnetic penetration depth in the planes ($`\lambda _{ab}`$) is obtained from $`M/\mathrm{ln}(H_a)=\varphi _0/(8\pi \lambda _{ab}^2)`$ for $`H_ac`$ ($`M=m_r/volume`$, $`\varphi _02.07\times 10^{15}`$ Vs). Since sample A shows a reversible magnetization already at very small fields (cf. fig. 3), $`\lambda _{ab}`$ can be evaluated in the whole temperature range from 5 K to $`T_c`$ (see fig. 2a). A fit of $`\lambda _{ab}^2(t)`$ leads to $`\lambda _{ab}(0)`$ = 82 nm and shows that the temperature dependence lies in between the (clean limit) BCS Muh59  and a typical strong coupling model Car90 . The deviation at lower temperatures indicates a smaller energy gap - to - $`T_c`$ ratio than according to the BCS theory, in agreement with other experiments (e.g. Giu01 ; Sza01 ), which can be explained by the two band (assuming a small and a large gap Bou01 ) as well as by the anisotropic gap model Haa01 . Further work on more comprehensive calculations including material dependent parameters are currently under way. The penetration depth in c - direction is obtained from $`\lambda _c=\gamma \lambda _{ab}`$, hence $`\lambda _c(0)=`$ 370 nm. The evaluation of $`\lambda _c`$ from the $`m(T)`$ measurements for $`H_aab`$ confirms the anisotropy, but is affected by comparatively large errors.

Further, the (GL) relation $`\mu _0H_{c2}^{ab}=\varphi _0/(2\pi \xi _{ab}^2`$) gives access to the coherence length in the ab - plane $`\xi _{ab}`$ and in the c - direction $`\xi _c=\xi _{ab}/\gamma `$ (fig. 2b). Accordingly, $`\xi _{ab}`$(0) = 10.2 nm and $`\xi _c(0)=2.3nm`$.

The lower critical field $`H_{c1}`$ can be calculated from $`\mu _0H_{c1}^x=[\varphi _0/(2\pi \delta \lambda _{ab}^2)][\mathrm{ln}(\delta \lambda _{ab}/\xi _{ab})+0.5]`$ ($`x`$ = c and $`\delta `$ = 1 for $`H_ac`$ and $`x`$ = ab and $`\delta =\gamma `$ for $`H_aab`$), leading to $`\mu _0H_{c1}^c(0)`$ = 63 mT and $`\mu _0H_{c1}^{ab}(0)`$ = 22 mT (fig. 2c). A direct experimental assessment of $`H_{c1}`$ is usually quite difficult, because only the penetration field $`H_p`$, i.e. the field, at which the first flux lines enter the sample, can be obtained, which depends on the sample geometry Zel94 , the anisotropy and the pinning force. We determined $`H_p`$ from measurements of the trapped magnetic moment, i.e. by measuring the moment in zero field after successively applying higher external fields and searching for the first deviation from zero at $`H_p`$ Boh97 . This procedure is still influenced by a finite critical current density Kuz97  and by geometry effects. For example, $`\mu _0H_p^c`$ 4 mT at 5 K (sample A) can be converted into $`H_{c1}(H_p)`$ for a rectangular sample geometry Doy97 , which leads to $`H_{c1}/H_p`$ 17.7 for $`\gamma =4.5`$, i.e. $`\mu _0H_{c1}^c`$(5 K) $``$ 70 mT, but overestimates $`H_{c1}^c`$ because the critical current density is not taken into account, and is not too far away from the calculated result of fig. 2c (62 mT at 5 K).

Furthermore, the thermodynamic critical field is calculated from the GL relation $`\mu _0H_c=\varphi _0/(\sqrt{8}\pi \lambda _{ab}\xi _{ab})`$ and found to be 0.28 T at 0 K. Because $`\mathrm{\Delta }f=\mu _0H_c^2/2`$ (condensation energy), it can also be obtained by integrating the reversible magnetization $`M(H_a)`$, i.e. $`\mathrm{\Delta }f=\mu _0_0^{H_{c2}}M𝑑H_a`$. The reversible magnetic moment is either calculated from the irreversible branches of the magnetization in increasing ($`m_+`$) and decreasing ($`m_{}`$) fields in the fully penetrated state, $`m_r=(m_++m_{})/2`$ (cf. fig. 3) or directly measured. The results of the numerical integration are shown in fig. 2d and denoted by $`H_ac`$ \- direct and $`H_aab`$ \- direct, respectively. A comparison with the GL results indicates that the London model for the magnetic penetration depth and the GL relations for $`H_{c2}`$ and $`\xi `$ represent excellent solutions for MgB2. The maximum difference at low temperatures is less than 2 %. To check the influence of uncertainties near $`H_p`$ in the direct evaluation (geometrical barrier, flux pinning), we replace $`M(H_a)`$ at 5 K by the separately measured Meissner slope at $`0H_aH_{c1}(1D)`$ and by a simple logarithmic behavior at $`H_{c1}(1D)H_aH_{c1}`$, i.e. we simulate the behavior of an ellipsoidal sample, where the ”effective demagnetization factor” $`D`$ is determined from $`M(H_a)=H_a/(1D)`$ in the Meissner regime. This procedure reduces $`H_c`$ at 5 K and brings the above difference to almost zero.

The deviation function, $`D(t)=[H_c(t)/H_c(0)][1t^2]`$, describing the deviation of $`H_c(t)`$ from the parabolic behavior (two fluid model) and indicating the coupling strength in a conventional superconductor, is shown in the inset of fig. 2d. The maximum of -0.3 - -0.9 % lies in between the weak ($``$ -3.5 %) and the strong coupling result ($``$ +2.5 % for Pb). Although we have to consider evaluation errors, the results indicate a clear deviation from the weak coupling model, even if we consider the anisotropy (cf. Haa01 ), and is consistent with other experiments (e.g. Bud01 ; Qui02 ).

The GL parameter $`\kappa =\lambda /\xi `$ is defined at $`T=T_c`$. At lower temperatures the Maki parameters Mak64  $`\kappa _1=H_{c2}/(\sqrt{2}H_c)`$ and $`\kappa _2=[0.5+0.43/(M/H_a)_{H_{c2}}0.43D]^{1/2}`$ can be used with $`\kappa _1(T_c)=\kappa _2(T_c)=\kappa `$. $`\kappa _1`$ ($`=\lambda /\xi `$ in the GL model) is shown in fig. 2e for $`H_ac`$. Linear extrapolations lead to $`\kappa _1^c(0)=8.1`$ and $`\kappa _1^c(T_c)=4.7`$. The ratio $`\kappa _1^c(0)/\kappa _1^c(T_c)`$ is 1.72 and considerably larger than the BCS value (1.26 in the clean and 1.20 in the dirty limit Hel66 ), but this is not unexpected considering stronger coupling Car90  and anisotropy. $`\kappa _2`$ depends on the slope of $`M`$ near $`H_{c2}`$ and allows a precise determination of $`\kappa ^c`$, which is again found to be 4.7 from a linear extrapolation to $`T_c`$. For $`H_aab`$, we get $`\kappa _1^{ab}=\gamma \kappa _1^c`$ and therefore $`\kappa _1^{ab}(0)=37.1`$ and $`\kappa _1^{ab}(T_c)=4.7`$. The errors in $`\kappa _2^{ab}`$ are relatively large in this case because of the very small slope of the magnetization near $`H_{c2}`$, but the extrapolation leads to $`\kappa ^{ab}=5`$, very close to $`\kappa ^c`$.

At last, we turn to the irreversible properties of the MgB2 single crystals. Hysteresis curves recorded at different temperatures are presented in fig. 3 for $`H_ac`$ and $`H_aab`$. They demonstrate the excellent crystal quality by the small hysteresis and the low irreversibility fields in both directions. Note that all data points presented in fig. 3 were measured in the fully penetrated state. According to the Bean model Bea62  ($`J_c`$ is assumed to be constant), the critical current density in the planes can be calculated from the irreversible magnetic moment ($`m_i=[m_+m_{}]/2`$). For rectangular samples we use $`J_c(B)=\{m_i(B)/\mathrm{\Omega }\}\{4/[b(1b/3a)]\}`$ (sample volume: $`\mathrm{\Omega }=abc`$), and get $`1.4\times 10^9`$ Am-2 at 5 K in the remnant state for both samples. To obtain the irreversibility line, the onsets of a difference between the field cooled and the zero field cooled $`m(T)`$ measurement were evaluated. The results of fig. 3 (inset) show that the irreversibility line is very low for both field directions.

In summary, we presented measurements of the magnetic moments in single crystalline MgB2 for fields $`H_ac`$ and $`H_aab`$, and the subsequent evaluation of the basic mixed state parameters. The most important results are summarized in table 1. The general consistency of the data set, which is documented nicely, e.g., by the results on the thermodynamic critical field, suggests that the standard theoretical description can be employed in MgB2. The data indicate that MgB2 is a low - $`\kappa `$ type II superconductor in the clean limit with an intermediate electron phonon coupling strength (cf. also Cho01a ; Cho01b ), but a very large anisotropy.

We wish to thank F. M. Sauerzopf for useful discussions and H. Hartmann for technical assistance. This work was supported in part by the Austrian Science Foundation (FWF project 14422), the Austrian Exchange Service (OEAD 27/2000), the European Commission (program ICA1-CT-2000-70018, Centre of Excellence CELDIS), the TMR Network SUPERCURRENT and the Swiss National Science Foundation.


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# Effects of gating and contact geometry on current through conjugated molecules covalently bonded to electrodes

## I Introduction

Studies of electron transport through organic molecules (molecular films), viewed as the possible components of molecular electronic devices, are a very active area of research . Although the rectifying properties of the molecules in two-terminal devices were demonstrated in 1990s, only recently have three-terminal devices based on a self-assembled monolayer (SAM) of simple conjugated molecules containing either one or two phenyl rings C6H6 or two or three thiophen rings C4H4S been fabricated. The molecules were gated from the edge of the vertical device through $`L=`$30 nm of SiO2 gate oxide (30 nm was the nominal oxide thickness, but the high-resolution transmission electron microscopy showed much thinner oxide barrier of 4-5nm ). In the slot geometry of this experiment, the drain current $`I_d`$ through only several thousand molecules close to the gate oxide should have been affected by the gate voltage $`V_g`$. The measured conductance $`dI_d/dV`$ at zero source-drain bias was about 5 $`\mu `$S/molecule. The gating field on the molecules should be small because the length of the molecules (the “channel” length) is tiny, $`2t=12`$ nm, so that the geometrical aperture factor is small, $`t/L1.`$ In spite of this, Schön et al. have initially estimated a dramatic change of conductance of the molecules by a factor to be about $`10^7`$ (it was later determined that the effect was overestimated, probably because of disorder and other factors in pure SAMs), with a large transconductance $`dI_d/dV_g=1213`$ mA/V for pure SAMs of biphenyl molecules and about 6 mA/V for phenyls at room temperature. Dilute systems of conducting molecules (namely, 4,4’-biphenyldithiol and some other species) embedded in a matrix of non-conducting alkanedithiols have also been measured with the aim to sample individual conducting molecules. Schön et al. have found that the conductance through the molecule is about 0.1$`\mu `$A/V at zero drain voltage $`V=0`$, and approaches one conductance quantum $`2e^2/h=77.5\mu `$A/V at relatively small gate voltage $`V_g0.3`$ V. The histograms of conductance measured on a series of devices suggested that the conductance through the gated molecules was quantized in the fundamental units of $`2e^2/h.`$ The conductance peak position varied with the gate voltage $`V_g`$ from device to device. The transconductance $`dI_d/dV_g`$ was found to be in the range of $`150\mu `$A/V at 4K, decreasing to about 10$`\mu A/V`$ at room temperature (in the earlier measurements the peak value of $`dI_d/dV_g`$ was estimated of about 13mA/V  for the biphenyl molecules). The corresponding modulation of conductance in the film of individual dithiol molecules has been estimated to be much larger than $`10^3`$. This is a huge effect indeed if it is to be explained by a mechanism related to the behavior of individual molecules.

Very recently this work has been extended to SAMs of benzene-(1,4)-dithiolate (-S-C6H4-S-), the simplest conjugated molecules, referred to below as BDT, with only one phenyl ring. The area of the measured device comprised about $`10^4`$ molecules, mostly non-conducting alkanes with a small fraction (10$`{}_{}{}^{4})`$ of the conducting BDT molecules. In this geometry, only one or a few BDT molecules should have contributed to transport. The first peak in BDT conductance has been found at a bias of about 2.1V with the corresponding value of 25$`\mu `$A/V . Interestingly, the conductance appeared to be much larger than that found in the earlier break-junction experiments by Reed et al. who observed the first peak in conductance of 0.05$`\mu `$A/V at 1.4V. Schön and Bao have also observed a jump in conductance from 0.7-1.0 $`\mu `$A/V to much larger values close to the conductance quantum $`77.5`$ $`\mu `$A/V at the gate voltage $`V_g0.4`$ V and the drain voltage of about $`0.7`$ V (this is a jump of almost two orders of magnitude). The position of this switching shows some hysteresis when the gate voltage is varied in the range $`0.6<V_g<0`$ V. This hysteretic behavior cannot possibly come from the individual molecule behavior and should be related to some extrinsic mechanism, as we shall discuss below. Also interesting is the observed change in the fine structure of the conductance: there is a series of small peaks 45 meV apart from each other on the conductance curve for $`V_g=0,`$ and the period shrinks down to 40 meV at $`V_g=0.5`$ V. Such peaks are usually attributed to tunneling assited by molecular vibronic excitations, so the change in the period indicates a possible change in molecular conformation. These abrupt changes cannot be explained by the electric field created by the gate, since the corresponding field on the molecule should be small.

With regards to a possible origin of the observed behavior, we first mention the importance of the geometry of the molecule-electrode contact. If the orientation of the molecule with respect to an electrode changes, so does its conductance. Indeed, we have found earlier that the conductance of BDT (or any other conjugated thiol-terminated molecule) strongly depends on the angle $`\theta `$ between the molecular “backbone” and the normal to the gold surface (Fig. 1). In a simple “toy” model, the current dependence is $`\mathrm{sin}^2\theta `$ in the regime of strong resonant tunneling (large bias) and even stronger, $`\mathrm{sin}^4\theta `$ in the regime of non-resonant tunneling (small bias). Note that the angular dependence of current is much stronger when the end sulfur is in the less-coordinated “top-site” position above a surface Au atom, compared to a “hollow-site” position, when it is bonded to three surface gold atoms, see Fig. 1. These bonding positions were considered in the literature as being the most favorable. Indeed, it has been provisionally suggested that the conformational changes of the BDT with respect to electrodes, discussed in , are responsible for the observed “switching” behavior of SAMFETs. Also, one cannot exclude that the observed changes in conductance through BDT are caused by charge trapping-detrapping processes close to the interface between the molecular layer and the gate SiO2.

## II Self-consistent calculations of electronic structure and transport

In order to gain more insight into the origin of the observed extraordinary dependence of molecular conductance on a weak gating field observed in Refs. , we have performed a series of self-consistent calculations for different attachments of the BDT molecule to Au(111) surface. We have found that the effects of charge redistribution as a function of molecular configuration and/or external field are important, since the mismatch between the work functions of Au and BDT results in a considerable charge flow between the molecule and gold electrodes. Without external bias, the lowest unoccupied molecular orbital (LUMO) lies closer to the Fermi level of Au compared to the highest occupied molecular orbital (HOMO). The current through the molecule strongly depends on both the tilting angle and the self-consistent charge redistribution across the molecule. Although it is not clear a priori what the sign of the combined effect would be, we have found that our previous conclusion about strong orientation dependence of the conductance through anisotropic conjugated $`\pi `$orbitals and the s-orbitals on electrode Au remains valid.

BDT attaches strongly to the gold substrate by thiolate end groups -S- that form covalent bonds with Au . In order to properly account for such a bonding in the present calculations, the Au atom(s) connected to S are treated separately from other gold atoms that compose the gold electrode. The conductance is computed with the use of the general procedure of Ref. . The gold electrodes are described by a tight binding model with nine $`s`$, $`p`$, and $`d`$orbitals per each Au atom with parameters from Ref. . The equilibrium molecular geometry is found by total-energy density functional minimization . The tight-binding parameters for the molecules and molecule-lead interfaces are taken from the solid-state table of elements .

The onsite energies in the present tight-binding model, which are very important for finding the correct charge redistribution between the molecule and the electrodes, have been estimated from the Hubbard model in the atomic limit. The energy of an isolated atom is approximated as $`E_m=E_0`$ $`ϵ\mathrm{\Delta }q_m+\frac{1}{2}U\mathrm{\Delta }q_m^2`$. Here $`E_0`$is the energy of a neutral atom with the atomic energy level at $`ϵ<0`$with respect to the vacuum level (energy origin), $`\mathrm{\Delta }q`$ is the excess charge of an atom, and $`U`$ is the intraatomic Coulomb repulsion. In this approximation, we obtain $`ϵ=\frac{1}{2}\left(A+I\right),`$ $`U=IA`$, where $`A`$ and $`I`$ are the experimental atomic values for the affinity and the ionization energy, respectively. These expressions have been used to estimate the following parameters used in the present work: $`U=11.5,`$ $`ϵ=7.8`$ for H; $`U=6.3,`$ $`ϵ=5.2`$ for C; $`U=7.8,`$ $`ϵ=6.5`$ for S; and $`U=6.7,`$ $`ϵ=5.9`$ for Au (all in units of eV). We would like to mention that the use of different values for the one-electron energies $`ϵ`$, like the ones from Ref. ) leads to unphysically large charge transfers.

We have calculated the current through BDT on Au(111) in both the top-site and the hollow-site positions. Including onsite and intersite Coulomb interactions one finds that the onsite one-electron energies for state $`a`$ at the site $`m`$ should be adjusted as

$$ϵ_{ma}=ϵ_{ma}^0+U_m\mathrm{\Delta }q_m+\underset{m^{}(m^{}m)}{}e\gamma _{mm^{}}\mathrm{\Delta }q_m^{}+e\varphi _m^I,$$
(1)
where $`ϵ_{ma}^0`$ are the onsite energies in a system with neutral atoms, $`\mathrm{\Delta }q_m`$ are the charges on sites, $`\gamma _{mm^{}}=1/|𝐦𝐦^{}|,`$ $`\varphi _m^I`$ the image potential, and $`e<0`$ is the electron charge. The charge $`\mathrm{\Delta }q_m`$ is found self-consistently from the local density of states, which is given by the site-projected imaginary part of the exact Green’s function of the problem. The total retarded Green’s function $`G_{mam^{}a^{}}(E)`$is calculated by “attaching” the semi-infinite leads to the molecule. As a result of the attachment the molecular levels acquire a width that strongly depends on the coupling between electrode and the molecule, $`\mathrm{\Gamma }t_{\mathrm{Au}\mathrm{S}}^2/D_{\mathrm{Au}}`$. Here $`D_{\mathrm{Au}}`$ is the width of the s-band for Au electrodes, $`t_{\mathrm{Au}\mathrm{S}}`$ is determined mainly by the $`sp\sigma `$ hopping integral from Au to the end sulfur atom on the BDT molecule, which is of the order of 1-2 eV. One should expect significant broadening of the molecular levels when the molecule is attached by a thiol group to Au, since a strong chemical bond is formed.

Under zero bias voltage, the electron charge $`q_m`$ on the site $`m`$ can be found from the Green’s function in the standard manner as

$`q_m`$ $`=`$ $`{\displaystyle \underset{a}{}}{\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑EN_{ma}(E)f(E),`$ (2)
$`N_{ma}(E)`$ $`=`$ $`{\displaystyle \frac{1}{\pi }}\mathrm{Im}G_{mama}(E),`$ (3)
where $`N_{ma}(E)`$ is the density of states $`a`$ on the site $`m`$, $`f(E)=\left(1+\mathrm{exp}\frac{EE_F}{T}\right)^1`$ is the Fermi function, and $`E_F`$ is the chemical potential found from the global charge neutrality of the system.

In the case of finite bias voltage the system is out of equilibrium and one has to find the charge that is “flowing-in” from the electrodes onto the molecule, cf. . Then the DOS on the site $`m,`$ related to the influx of electrons from the lead $`w=1,2\mathrm{},`$ is written as $`N_m^w(E)=2(\mathrm{for}\mathrm{spin})_{k_z^w𝐤_{||}^w}\left|\psi _m(k_z^w,𝐤_{||}^w)\right|^2\delta \left(EE_{k_z𝐤_{||}}^w\right),`$ where $`\psi _m^w(k_z,𝐤_{||})`$ is the wave function at the molecular site $`m`$, which asymptotically becomes an incident Bloch wave in the lead $`w`$ far from the molecule with the wave vectors $`(k_z,𝐤_{||})`$. Now we can find the occupation number for that site on the molecule due to charge flowing in from the lead $`w`$ as $`q_m=_w_{\mathrm{}}^{\mathrm{}}𝑑EN_m^w\left(E\right)f_w(E),`$ where $`f_w(E)`$ is the Fermi function for the $`w`$th lead (i.e. with $`E_F=E_{Fw}`$). In order to calculate the Green’s function (and the charges $`q_m`$) we define the “channels” such that $`k_z=k_{zl}^w(E),`$ where $`l=1,M`$ enumerates all the quantum states in the lead unit cell (slice) . It is convenient to re-write the expression for the charges in terms of “open channels”. The “open channel” is defined as a Bloch wave which propagates in the lead at a given energy. The Bloch waves incident on the molecule (i.e. having the velocities towards the scatterer, $`v_l>0`$) will contribute to the charge flowing to the molecule from a particular lead:

$`N_m^w(E)`$ $`=`$ $`2{\displaystyle \underset{𝐤_{||}^r}{}}{\displaystyle \frac{1}{2\pi }}{\displaystyle _{\pi /d_z^w}^{\pi /d_z^w}}𝑑k_z^r\left|\psi _m(k_z^w,𝐤_{||}^w)\right|^2\delta \left(EE_{k_z𝐤_{||}}^w\right)`$ (4)
$`=`$ $`2{\displaystyle \frac{1}{2\pi }}{\displaystyle \underset{𝐤_{||}^w}{}}{\displaystyle \underset{l\left(v_l^w>0\right)}{}}{\displaystyle \frac{1}{\mathrm{}v_l^w}}\left|\psi _m^w(k_{zl},𝐤_{||})\right|^2,`$ (5)
where $`d_z`$ is the unit cell length along the lead. $`\psi _m^w`$ are normalized for the length of the wire, which drops out of the final answers. Note that the integration in (5) goes over the whole Brillouin zone, not just over $`k_z>0`$. The delta-function picks up the open channels on the leads. From now on we can drop the lead index and assume that one can later sum up all the charges flowing from all the leads. Once the Hamiltonian is set up, one calculates the charges on the sites, recalculates the onsite energies $`ϵ_{ma}`$ and continues iteratively until the charges converge.

The current through the film is given by a standard expression

$$I=\frac{2q}{h}𝑑E\left[f\left(E\frac{qV}{2}\right)f\left(E+\frac{qV}{2}\right)\right]T(E),$$
(6)
where $`q=|e|`$ is the elementary charge, and $`T(E)`$ is the transmission probability

$$T(E)\underset{𝐤_{},nn^{}}{}\left|t_{nn^{}}(E,𝐤_{})\right|^2,$$
(7)
where the summation goes over the surface Brillouin zone of the lead. Transmission coefficients $`t_{nn^{}}(E,𝐤_{})`$ between the scattering channels $`n`$ and $`n^{}`$ are found from the solution of the scattering problem. In the case of weak molecule-electrode bonding the transmission probability is approximately given by the Breit-Wigner formula

$$T(E)\underset{r}{}\frac{\mathrm{\Gamma }_{rL}\mathrm{\Gamma }_{rR}}{\left(EE_r\right)^2+(\mathrm{\Gamma }_{rL}+\mathrm{\Gamma }_{rR})^2/4},$$
(8)
where $`E_r`$ enumerates the energies of the molecular orbitals (MOs) contributing to transport (not all of them do, see Figs. 2, 3), $`\mathrm{\Gamma }_{rL(R)}/\mathrm{}`$ is the rate of the carrier transfer to the left (right) electrode from the molecular orbital $`r`$. This formula applies when the width of the MOs is much smaller than the energy difference between them, so that the resonances do not overlap. Each conducting molecular orbital produces a step-like contribution to the current. Indeed, when the resonance falls into the “window” between the lowest and the highest Fermi levels in the leads $`E_{FL}<E_r<E_{FR}`$, the current obtained from Eq. 6 is

$$I\frac{2q}{\mathrm{}}\frac{\mathrm{\Gamma }_{rL}\mathrm{\Gamma }_{rR}}{\mathrm{\Gamma }_{rL}+\mathrm{\Gamma }_{rR}}.$$
(9)
It follows from this analysis that the current-voltage characteristic should look as a series of steps, occurring when the resonant conditions are satisfied for particular conducting molecular orbital. The apparent negative differential resistance (NDR) at bias above 2V, Figs. 4-6, results not from resonant tunneling but from the electrode density of states. In the present model the electrode DOS in bounded from above for each particular value of $`𝐤_{}.`$ As a result, the current will be zero at the energies above some threshold. The apparent NDR persists in the present calculations irrespectively of the number of basis functions (s-, sp-, or spd-basis), Fig. 6.

## III Effects of contact geometry and gating on current-voltage characteristics

We argue below that gating of SAMs in the experiments  may have led to changes in molecule-electrode geometry and, consequently, to large changes in conductance. Given the strong orientational dependence of the current through conjugated molecules like BDT, and that in experimental SAMs the molecules are never positioned strictly normal to the electrode surface (as was assumed in Refs.), we shall present the results for the transmission, density of states (Figs. 2, 3) and I-V curves (Figs. 4-6) for a series of tilting angles $`\theta `$ between the backbone of the molecule and the normal to the Au(111) surface. The $`\theta `$dependence of the I-V curves for BDT on the top site and hollow site is illustrated on Figs. 4,5 for $`\theta =030^{}`$. It is especially strong for BDT on the top site. The majority of the results is given for $`\theta =10^{},`$ which seems to be a reasonable choice for experimental SAMs. Note that in the upright position $`\theta =0`$ in top site (i.e. perpendicular to the contact surface, as was assumed in Ref. ) the overlap between the S $`x`$ and $`y`$ p-orbitals ($`xy`$ being in contact surface plane, $`z`$ normal to the contact) and the s-orbital on Au (or jellium) is exactly zero by symmetry, since $`(x|H|s)=(y|H|s)0,`$ where $`H`$ is the Hamiltonian. The s-electron on the top Au can only hop onto a S $`z`$-orbital via a $`(z|H|z)=ss\sigma `$ hopping integral. Obviously, for BDT on the top site, this result holds for all incident electrons with any $`𝐤_{}.`$ Therefore, the $`x`$ and $`y`$ p-orbitals on S cannot be traversed by electrons incident from the contact. At the same time, only those states on the sulfur ion are coupled to conjugated $`\pi `$orbitals on the benzene ring. Therefore, for the BDT on the top site and oriented normal to contact, the current will be suppressed, as observed in calculations by Di Ventra et al.. Obviously, this symmetry selection rule is lifted for any $`\theta 0`$. Thus, the previous calculations  have been performed at an artificial singular point. Incidentally, the same conclusion applies to the scattering of the carriers incident with $`𝐤_{}=0`$ (surface $`\mathrm{\Gamma }`$point) on upright BDT on a hollow site. Indeed, in this case the matrix element for hopping to the sulfur atom on the molecule is proportional to $`_i(x_i|H|s)\mathrm{exp}(i𝐤_{}\rho _i)_il_i=0`$ for $`𝐤_{}=0,`$ where $`l_i`$ are the directional cosines connecting the center of the triangle formed by three Au atoms on Au(111) surface with Au atoms in the corners at positions $`\rho _i`$. The same is obviously true of the hopping to the $`y`$ p-orbital on S. Thus, in the case of BDT on a hollow site, all the contribution to the current comes from states with $`𝐤_{}0.`$ Therefore, for BDT placed upright on the hollow site, the total current is not suppressed, as it is for BDT on the top site. Consequently, the current for BDT on the hollow site is considerably less sensitive to the precise contact geometry.

### A Density of states and transmission

Most of the present results can be appreciated from the analysis of the transmission probability $`T(E)`$ and the density of states $`N(E)`$on the BDT molecule, see Figs. 2,3. One expects from the golden rule that the transmission would be proportional to the density of states. However, although peaks of both functions follow each other rather closely, there are important differences between the density of states and the transmission. It is easier to analyze the results for the top position first. There are two sharp peaks around the Fermi level $`E_F`$, marked as $`\pi ^{}`$ (at $`E_\pi ^{}=E_F+0.5`$ eV) and $`\pi `$ (at $`E_\pi =E_F1.0`$ eV), Fig. 3(a). Transmission is almost zero at $`E>E_\pi ^{},`$ but there is a large density of non-conducting  states in this energy interval. Those non-conducting states are formed at the end of the molecule and reside primarily on the end sulfur atom and gold atom on top of which the molecule sits, with little coupling to C$`\pi `$ conducting states on the ring. The $`\pi ^{}`$ peak contains mostly Au and S states and some C$`\pi `$ ring states whereas the $`\pi `$ peak is made mostly of S and C$`\pi `$ ring states with a little addition of Au states. Sulfur atoms introduce the states in the HOMO-LUMO gap of the benzene ring (which is about $`6.5`$ eV) and hybridize with C$`\pi `$ states to make the conducting pathways across the BDT molecule. As a result, we see a much smaller gap between $`\pi `$ and $`\pi ^{}`$ states in BDT, which is $`E_\pi ^{}E_\pi =1.2`$ eV. In the case of the hollow-site position, the situation is considerably different. There the $`\pi `$ and $`\pi ^{}`$ states are much broader and pushed apart by much stronger hybridization with three underlying Au atoms than for the top site, Fig. 3(b). The “soft” energy gap for the hollow position is $`E_\pi ^{}E_\pi =3.25`$ eV, Fig. 3 (a) (cf.).

It is instructive to compare the present results with the recent data for Ni-BDT-Ni SAMs  and jellium-LDA calculations. The systems should have many similarities since Au and Ni have almost the same work function of about 5.1 eV. In both systems a large conductance peak is observed at a bias of about $`V=2.1`$V, which is larger than the earlier value of 1.4V . The peak in Ni system is narrower and does not show any appreciable spin splitting. Interestingly, in Ni-BDT-Ni the additional resonant-like features are found at low bias voltages of about 0.3 V and 0.9 V. They correspond to smaller conductance compared to the peak at 2.1V. The position of the peaks should be compared with that of Ni d-states. It is well known that the energy of a minority peak in Ni DOS is very close to the Fermi level, whereas the majority peak is about 0.5eV below $`E_F`$. If the conducting molecular states were considerably smeared out, like in the case of hollow position, Fig. 2, then the observed low-bias features might be due to those peaks in Ni d-DOS. The fact that the first peak is observed at 0.3V, and not much smaller bias, may be due to energy dependence of the molecular density of “tail” states at $`E_F`$, which shifts the peaks by 0.3V. If, on the other hand, the peaks in the molecular density of states are sharp, like in the case of top position, Fig. 2, then the peaks in conductance should correlate with the position of the molecular orbital closest to the Fermi level (LUMO, according to the present work). The position of the LUMO in BDT in the present model is about 0.5 eV above the Fermi level for the top position. Therefore, we expect that in the top-site configuration there should be two peaks in the conductance, one at about 0.5-1.0 V (the position of the d-peak in Ni DOS with respect to the $`\pi ^{}`$ resonance, depending on the connection between the molecule and the electrodes) and another at about 0.5 V higher than the first one (at 1.0-1.5 V). Interestingly, this is very similar to what was observed experimentally for the Ni-BDT-Ni system, with the peaks at $`V=0.3`$ V and $`0.9`$ V . If, on the other hand, the LUMO ($`\pi ^{}`$ state) is at 1eV above the Fermi level, than the spin-peaks in Ni d-DOS might have produced the peaks in conductance at 2-3V. Indeed, there is a conductance peak at 2.1V in both Ni- and Au-based systems, but it is not spin-split in the case of Ni electrodes. It is worth mentioning that the position of the first peak in conductance is a strong function of the tilt angle, and it may vary significantly, Fig. 4. Finally, we note that the HOMO-LUMO gap in the “jellium” calculations is $`5`$ eV , which is substantially larger than that in bare BDT molecules, and that is unlikely. The calculated value of the first peak in conductance in jellium-LDA is 2.4V, larger than the observed value of 2.1V. This suggests that the calculated gap is larger than the measured one, which is contrary to the usual notion that the LDA gaps are smaller than the experimental ones due to insufficient account of electron-electron correlations. As follows from this discussion, one needs more analysis to draw definitive conclusions about the position of the lowest conducting orbital with respect to the Fermi level in electrodes in Au-BDT-Au and Ni-BDT-Ni.

### B Gating the molecules

The gating effect on the transmission and I-V characteristics is illustrated in Figs. 4,5. The gating is modeled by shifting the on-site energies on the molecule by $`\mathrm{\Phi }_g`$, which is usually $`0.5`$, $`0`$, and $`0.5`$ eV in the calculations. Obviously, in the experimental situation  such a large shift would require very large gating fields, comparable to the atomic fields in the order of magnitude. This is because one has to substantially change the electronic states on the molecule, and the characteristic energy is given by the HOMO-LUMO gap, usually a few electron-volts. Such large fields could not be possibly produced in the slot geometry with the channel length of only $`t=12`$ nm through the gate oxide with thickness $`L=45`$ nm . Schematic of this gate is shown in inset in Fig. 4(a). The analytical solution to this electrostatic problem can be found by standard methods and it naturally contains a small parameter $`t/L1,`$ so the gating on the molecule itself would be much smaller than the nominal gating voltage $`V_g.`$

One can speculate that large gating may result from e.g. charge accumulation in the gate oxide next to the molecular film. However, changing the oxide from SiO2 to Al2O3 apparently has not modified the results. Besides, there is an abrupt change of conductance by about an order of magnitude at the gate voltage $`V_g=0.3`$V, which would suggest a high sensitivity of the interface charge to the bias voltage. Both facts are difficult to reconcile with the idea of interface charge accumulation but we will study this possibility.

Comparing Figs. 4(a) and 5(b), one observes that the smaller hybridization between S p- and Au s-states for BDT on the top site produces sharp features in the energy dependence of the transmission at the Fermi level. The LUMO in this case is above the Fermi level by only about 0.5eV. The shifts of on-site energy by similar amount substantially change the transmission at the Fermi level, Fig. 4(a), and the corresponding current per molecule as shown in Fig. 5(a). There is a pseudogap at low voltages $`V1`$V, with the threshold voltage moving by an amount comparable to the external shift $`\mathrm{\Phi }_g`$ for the top-site configuration. By contrast, the large hybridization of S p-states with Au on the hollow site results in much broader energy tails of the resonant peaks in the density of states in the gap region in the vicinity of the Fermi level. Consequently, gating effect on the transmission, Fig. 5(b), and current, Fig. 5(b), is smaller compared to the top-site situation.

For the hollow-site configuration there is no trace of the HOMO-LUMO gap in the I-V curve, and the I-V curve is almost ohmic in the wide range of voltages $`V<2`$V (Fig. 5). This is indicative of the metalization of the chemically bonded molecule. This should have general implications, the simplest being an obvious difficulty in gating such molecules. This relates well to the large observed values of conductance (close to a conductance quantum) through a single molecule, and its small temperature dependence .

Finally, it is important to mention that in the present as well as other calculations, the LUMO is the closest molecular orbital to the Fermi level $`E_F`$ and the maximum gating effect is naturally expected when its energy is pulled down closer to $`E_F.`$ This takes place at positive gating voltage, and not the negative one, as observed experimentally. This is an apparent contradiction which needs to be resolved.

### C Effect of contact geometry

The tilting angle has a large effect on the I-V curves of BDT molecules, see Figs. 4, 5. The behavior of the BDT on the top site and on the hollow site is again rather different. The I-V curve for the hollow site remains ohmic for tilting angles up to 75 with moderate changes of conductance, Fig. 5(b). The variation of the current with the angle $`\theta `$ are much larger for the top site, Fig. 5(a). By changing $`\theta `$ from 5 to just 15, one drives the I-V characteristic from one with a gap of about 2V to the ohmic one with a large relative change of conductance. Even changing $`\theta `$ from 10 to 15 changes the conductance by about an order of magnitude.

Finally, Fig. 6 illustrates the role of the electronic structure of the electrodes. The results described above have been obtained with only the s-states on Au atoms. We have also considered an sp- and spd-basis for Au. Although substantially increases the computing time, but the addition of p- and d-states brings about only moderate changes in current. Since the hybridization is different for different cases, the current magnitude slightly varies for different basis sets.

### D Possible origins of the observed gating effect

With regards to the origin of the observed gating effect, one can envisage that in dilute BDT-alkane solution sandwiched between Au electrodes there may be two processes going on that significantly change conductance. Since the BDT molecules are clamped by the matrix of alkane chains, they have to move with it. Note that the matrix of alkane chains is not in registry with the Au electrode. The BDT molecules have a nominal length of 7.2Åand are dissolved in the matrix of (CH2)5S alkanethiol insulating molecules with a nominal length of 8.3Å. Thus, the BDT molecule would appear as a dip on the surface of the matrix, and one or a few gold atoms can get into this dip during the deposition and bind to the end S. The geometry of this bond is uncertain, and the bond may well be stretched. In this case even a slight perturbation exerted on the SAM might lead to reconfiguration of the bond resulting in large changes of conductance. It seems reasonable to assume that the “domain walls” separating different patches in an alkane matrix move rather freely in the system, since it does not require much energy. The BDT molecules will follow the matrix and can either snap from a hollow site to a top site and back and/or change the tilt angle. Both processes may be accompanied by large changes in the conductance. Conformational changes of the clamped BDT molecule are rather restricted, and the motion of the “domain walls” may be quite repeatable. One may wonder what causes the domain walls to move. As a possible reason, we suggest the presence of positive metal ions inside the organic film, as a small concentration of electrode ions in a SAM is rather inevitable. Indeed, Au+ strongly interacts with C6H6 in the gas phase and forms an Au$`{}_{}{}^{+}`$C6H6 complex with a binding energy 2.65 eV, whereas neutral Au forms a Van-der-Waals complex with the binding energy 90 meV. Even more likely is a formation of those complexes with thiophenes, which carry an electric dipole. It is likely that a similar charged complex can form with BDT molecules in a SAM with those BDT molecules that have lost or are in poor contact with the gold substrate. It is also possible that a charged complex can be formed between the charged metallic ions (Au+ or other electrode metals) and alkane chains. A small field in the organic film will then produce a tangential force on the ions, and this may trigger the domain wall motion when the pinning is weak. Additionally, since the packing of the film is not ideal (an organic film is usually a rather disordered patchwork of “grains”), the Maxwell force acting on the top Au electrode at finite drain voltage and/or electron wind force may trigger the domain wall motion, which may also require a combination of these factors. The second possibility would be a build-up of the interface charge, but apparently the replacement of oxide did not change the results. As mentioned above, it is also difficult to explain the jump in conductance at a certain value of the gate voltage.

## IV Summary

We have presented an extensive analysis of the electronic states and transport through the benzene-dithiolate molecule, which is the simplest conjugated molecule that forms a SAM and exhibits large changes of conductance under gating. It shows that the effect of gating strongly depends on the geometry of the molecule-electrode contact, and is maximal for the less coordinated top-site position. It is related to the sharpness of the peak in transmission, which corresponds to the LUMO on BDT and is close to the Fermi level $`E_F`$ of an Au electrode. By the same token, the current is more sensitive to the tilting angle of the molecule when it is positioned on the less coordinated top site. It is worth mentioning that the fact that the LUMO is closer to $`E_F`$ suggests that a positive gating voltage $`V_g`$ should produce the larger effect, not a negative gate voltage, as was observed in . This discrepancy should be addressed in the future. Binding on the highly coordinated hollow site naturally leads to large hybridization of the molecular states with electrode states, which become smeared out. Consequently, BDT molecule becomes metallized, i.e. the I-V characteristic becomes practically ohmic. A very small effect of gating is predicted for this geometry. In any case, it is difficult to explain the large observed effect of gating on BDT molecules in a slot with a width of only 1 nm by small voltage applied to the gate 4-5 nm away. One should assume that there is either (i) a build-up of interface charge in the immediate vicinity of the slot opening, which is very sensitive to the gate voltage; or (ii) small inhomogeneous electrostatic forces and resulting stresses on the SAM result in the reconfiguration of the film and, consequently, of a clamped inside BDT molecule with respect to the gold contacts. Both of those mechanisms have problems of their own in explaining the experimental observations, as discussed in the text. Changes in random charges in the film and/or chemical composition of the BDT molecules (e.g. loss of end sulfur) are possible but are unlikely to be reversible. One needs to characterize the films better and vary the gate oxide thickness and other parameters of the system in order to confirm one of those mechanisms or suggest some other effects controlling the gating in slot geometries like the one used in Refs. .

We thank J.H. Schön for extensive helpful conversations and sharing his data and preprints, and R.S. Williams for useful discussions. The work has been partly supported by DARPA.


text:
# Universal behaviour in the floating up of quantum Hall extended states as B → 0

## Abstract

We investigate the relationship between the quantum Hall extended states and the apparent $`B=0`$ ‘metal’-insulator transition in extremely low density, high quality two-dimensional n-GaAs systems ($`\mu _{peak}2\times 10^7`$ cm2V-1s-1). The combination of small effective mass and high quality allow us to resolve the continued floating up in energy of the extended states down to very low magnetic fields, B=0.015T, despite an apparent ‘metal’-insulator transition at B = 0. We present a modified global phase diagram which brings together conflicting data in the literature from different material systems, and reconciles the differences as to the fate of the extended states as $`B`$ 0.

PACS numbers: 71.30.+h, 73.43.-f

There has been intense interest in the unexpected metallic behaviour observed in dilute two dimensional (2D) electron and hole systems. While the one parameter scaling theory of localization  predicts that in the absence of a magnetic field all 2D systems are insulating at $`T`$ = 0, an anomalously strong ‘metallic’-like behaviour ($`dR/dT>`$ 0) has been observed in various high quality, strongly interacting (large $`r_s`$) systems over the last few years . Although this temperature dependence suggests the possibility of a ‘metallic’ ground state, recent experiments  have shown that even in the ‘metallic’ phase there are logarithmic localising corrections which appear to drive the conductivity to zero as $`T`$ 0. If these corrections are not overcome by strong interaction effects  the results indicate that the ‘metallic’-like behaviour of $`dR/dT`$ may only be a finite temperature effect and the system is insulating at $`T`$=0. Despite numerous experimental and theoretical proposals the questions of what causes ‘metallic’ behaviour at finite temperatures, and if a 2D system can be a true metal at $`T`$ = 0, remain a subject of controversy.

Experimentally it is not easy to attain temperatures below a few tens of millikelvin, making the detection of logarithmic insulating behaviour in high quality samples where ‘metallic’ behaviour is observed difficult. Another way to determine the ground state is to relate what happens to the extended states in the quantum Hall regime at finite magnetic fields to the apparent ‘metal’-insulator transition (MIT) at $`B`$ = 0 . If there are extended states below the Fermi energy at $`B`$ =0 then the system will be metallic at $`T`$ = 0, otherwise it is an insulator. Since the one parameter scaling theory  shows that non-interacting 2D systems are always localised, Khmelnitskii  and Laughlin  argued that the quantum Hall extended states ‘float up’ in energy as $`B`$ 0, so that only localised states remain below the Fermi energy. This floating up has been observed in disordered n-GaAs and p-Ge systems that are insulating at $`B`$ = 0. However, recent studies of high quality p-GaAs systems, which exhibit ‘metallic’ behaviour at $`B`$ = 0, indicate that the Landau levels remain at a finite energy as $`B`$0 , suggesting a link between the $`B`$ = 0 ‘metallic’ behaviour and the quantum Hall extended states.

In this paper we track the evolution of the quantum Hall extended states as $`B`$ 0 in extremely high quality GaAs electron systems that exhibit an apparent MIT at $`B`$ = 0. Two different samples from undoped GaAs/AlGaAs heterostructures, where carriers are induced with a gate bias , were studied. These samples are amongst the highest quality systems in which the 2D MIT has been observed ($`\mu _{peak}2\times 10^7`$ cm2V-1s-1). The main difference between the samples is the lowest carrier density reached: $`5\times 10^9`$ cm-2 in sample A and $`3\times 10^9`$ cm-2 in sample B. Most significantly the electron effective mass ($`0.067m_e`$) is low compared to other semiconductor systems, and since the Landau level separation scales as $`eB/m^{}`$ we are able to follow the Landau levels to very low magnetic fields – precisely where ‘floating up’ should be most pronounced.

Figure 1 shows the resistance of sample A as a function of temperature at $`B`$ = 0 for different carrier densities on both sides of the ‘metal’-insulator transition. At low densities $`n_s=(57.1)\times 10^9`$ cm-2, the sample shows insulating behaviour where $`R_{xx}`$ increases as $`T`$0. As the density is increased to $`7.8\times 10^9`$ cm-2 the resistance exhibits non-monotonic behaviour, with insulating-like behaviour ($`dR/dT<0`$) at high temperatures and ‘metallic’-like behaviour ($`dR/dT>0`$) at lower temperatures (Fig. 1(c)). The change in sign of $`dR/dT`$ occurs at $`T/T_F`$ 0.1, where $`T_F`$ is the Fermi temperature. This non-monotonic behaviour is due to the system becoming non-degenerate  as has been observed in other material systems when $`T/T_F`$ 0.1 - 0.7 . As the density is increased further, to $`9.8\times 10^9`$ cm-2, the sample shows ‘metallic’ behaviour over the complete measurement range with the resistance dropping as $`T`$ 0 (Fig. 1 (d)). The ‘metallic’-like drop in resistance in this sample ($`5\%`$) is consistent with other studies where a decrease of anything between $`3\%`$  and a factor of eight  has been observed.

Having demonstrated the existence of an apparent ‘metal’-insulator transition at $`B`$ = 0, we now turn to examine the evolution of the extended states in the quantum Hall regime as $`B`$ 0. Measurements of the magnetoresistance $`R_{xx}`$ at different temperatures are used to identify the quantum Hall liquid-insulator transitions, using two well-established methods . This approach has the advantage that the transitions between quantum Hall and insulating states define a quantum critical point and provides an independent means of determining the ground state of the system at $`B`$ = 0. In the first method, $`R_{xx}(B)`$ is measured at a fixed carrier density for different temperatures. Typical traces are shown in Figs. 2(a-c) for densities that are insulating at $`B`$ = 0. The arrows mark the temperature independent points, corresponding to the centre of the Landau levels which separate the insulating state ($`dR/dT<`$ 0) at low $`B`$ from the quantum Hall liquid ($`dR/dT>`$ 0) at intermediate $`B`$. In the second technique, the density dependence of $`R_{xx}`$ is measured for different temperatures at a fixed $`B`$ (Figs. 2(d-f)). At ‘high’ magnetic fields ($`B`$ 0.04 T), the resistance depends strongly on temperature, yielding clear transitions from insulating to ‘metallic’ behaviour (indicated by the arrow in Fig. 2(d)). However, at lower magnetic fields (Fig. 2(e)), the separation between the Landau levels is much smaller. This makes it difficult to identify the transitions, particularly for these high quality n-GaAs samples where only a small change in $`R_{xx}`$ is observed over the measurement temperature range. While it is tempting to use this method to go to even lower fields and make a direct link to the apparent MIT at $`B`$ = 0 (Fig. 2(f)) , it is not experimentally possible to track the Landau levels below 0.015 T. This is due to the fact that the Landau level separation at these small fields becomes comparable to the thermal broadening (at $`B`$ = 0.01 T, $`\mathrm{}\omega _c4kT`$ at $`T`$ = 50 mK).

To track the evolution of the Landau levels in magnetic field, we have repeated these measurements at many different carrier densities and magnetic fields, and plot the position of the $`T`$-independent points in Fig. 3(d). Solid symbols mark points determined from the fixed density measurements while open symbols are obtained from fixed field measurements. Good agreement is obtained between these two techniques, and the data in Fig. 3(d) clearly shows that for $`B<`$ 0.05 T the extended states float up rapidly as $`B`$ 0. The power of this technique is that these transition points are $`T`$-independent and should therefore persist down to $`T`$ = 0 since they mark a quantum phase transition between quantum Hall liquid and insulating states. However at extremely low magnetic fields it is no longer possible to resolve the Landau levels and this technique is not valid. In particular there are no Landau levels at $`B`$=0, and whilst there is an apparent transition in Fig. 2(f) it is not known if it persists to $`T`$ = 0 . It is therefore crucial to track the quantum Hall transitions to as low a magnetic field as possible to shed light on the $`B`$ = 0 ground state.

In these experiments we have tracked the extended states down to the lowest fields that they can be resolved ($`B`$ = 0.015 T), and find that they float up continuously with no signs of saturation as $`B`$ 0. Furthermore the slope $`dn_s/dB`$ of the Landau level trajectory at these small fields ($`0.015<B<0.05`$ T) is more that an order of magnitude larger than previous studies in p-GaAs . The observation that the extended states start to float up so rapidly as $`B`$ 0 makes it difficult to relate the quantum Hall extended states in finite magnetic fields to the apparent $`B`$ = 0 MIT at $`n_s^c=(8.0\pm 0.25)\times 10^9`$ cm-2 , since this would require a sharp change in the trajectory of the extended states below 0.015T.

To compare these results with previous studies we show in Figs. 3 (a-c) similar data from disordered n-GaAs , disordered p-Ge , and high quality p-GaAs . In both of the disordered systems no apparent ‘metallic’ behaviour is observed at $`B`$ = 0, and the Landau levels float up rapidly as $`B`$ 0. However in p-GaAs, where ‘metallic’-like behaviour is observed at B=0, the Landau levels start to float up, but then appear to saturate to a finite density as $`B`$0. This observation has led to the suggestion that there is a relation between the quantum Hall effect and the ‘metallic’ behaviour observed at $`B`$ = 0 in these systems .

To resolve the discrepancy between the various experiments as to the fate of the extended state as $`B`$0 we must consider both the effects of disorder and finite temperature. It is known that the Landau levels start to float up when $`\omega _c\tau =\mu B`$ 1 . In disordered n-GaAs (Fig. 3(a)) this floating up occurs at relatively high magnetic fields $`B`$ 2.8 T such that the small effective mass makes it easy to resolve the Landau level separation $`\mathrm{}eB/m^{}`$. For disordered p-Ge in Fig. 3(b) the effective mass is higher, but the strong disorder still means the floating up occurs at large fields, $`B`$ 2 T, where the Landau levels are easily resolved.

The floating up becomes more difficult to observe experimentally in high quality samples (where the apparent $`B=0`$ metallic behaviour occurs) since we require very low temperatures, $`kT\mathrm{}eB/m^{}`$, to avoid thermal smearing. In the high quality p-GaAs of Fig. 3(c) the low disorder means that the levels only start to float up at low magnetic fields, $`B`$=0.4 T, where due to the large hole mass the Landau level spacings are already inherently small and thermal broadening becomes significant. The vertical dotted lines in Fig. 3(a-d) mark the magnetic fields below which it is not possible to track the Landau levels, because the level separation becomes comparable to the thermal broadening at 50mK. This line clearly shows that resolving the Landau levels below $`B0.08`$ T is problematic for the high quality p-GaAs sample in Fig. 3(c). However for low disorder n-GaAs the small electron mass makes it possible to safely track the Landau levels to much smaller magnetic fields, as can be seen in Fig. 3(d). Here we can reach magnetic fields as low as $`B`$ 0.015 T before thermal broadening sets in, and down to these low magnetic fields there is no sign of saturation. For completeness we have also marked the apparent $`B`$ = 0 transition, but re-iterate that unlike the quantum Hall transitions at finite $`B`$, it is not known if this transition persists to $`T`$ = 0. Significantly, this is the first time that continuous floating up of the Landau levels has been observed in high quality samples that exhibit ‘metallic’ behaviour at $`B=0`$.

Although both p- and n-GaAs show floating up of the Landau levels, an apparent discrepancy still remains. In Fig. 3(c) it might appear that at intermediate fields ($`B`$ = 0.2 T) the Landau levels start to saturate before thermal broadening sets in. However, we will show that it is not simply how low in magnetic field we can track the Landau levels, but how small $`1/\nu `$ is (where $`1/\nu =eB/hn_s`$), that defines the trajectory of the extended states as $`B`$0. In Figure 4 we present a global phase diagram which reconciles the experimental data from these different material systems with differing degrees of disorder. This diagram is based on the global phase diagram (GPD) of Kivelson, Lee, and Zhang  (shown in the inset) modified to highlight the floating up of the Landau levels in energy. In the GPD (where the $`x`$ and $`y`$-axis are $`1/\nu `$ and disorder) ‘floating up’ of the Landau levels in energy as $`1/\nu `$ 0 is equivalent to a ‘floating down’ of the quantum Hall liquid-insulator phase boundary in disorder. To relate data from different material systems we have normalised for the effective mass (since disorder $`1/\tau \rho _{xx}/m^{}`$), and plot the Landau level trajectories from several studies  in the $`1/\nu `$$`1/`$disorder plane. The resulting phase diagram in Fig. 4 demonstrates that the data from these different material systems, with sample disorder varying by three orders of magnitude, lie approximately on the same curve. This important result demonstrates that the phase diagrams constructed by *eight* different studies *are in fact consistent with each other*, and that it is possible to draw very different conclusions regarding the fate of the extended states as $`B`$ 0 depending on the lowest accessible value of $`1/\nu `$. To clarify this further, if we were to delete all the data below $`1/\nu `$ = 0.2 in Fig. 4, then *all* studies (even in systems with no $`B`$=0 MIT) would appear to show that the Landau levels do not float up indefinitely as $`B`$ 0, but saturate to some finite value. It is only possible to determine the ultimate fate of the extended states by going to very low values of $`1/\nu `$ $`(1/\nu 0.1)`$.

In summary, we present two significant new findings concerning the relationship between the $`B=0`$ MIT and the quantum Hall effect: (1) Using high quality n-GaAs systems we have observed that the extended states that exist in finite magnetic field float continuously up in energy as $`B`$ 0, despite an apparent ‘metal’-insulator transition at B = 0. (2) Most importantly, when plotted on a modified form of the Kivelson, Lee and Zhang global phase diagram, the Landau level trajectories from this and previous studies in different material systems are in fact consistent with each other, showing that the extended states always float up in energy as $`B`$ 0, irrespective of whether there is a $`B`$=0 MIT or not. The phase diagram highlights the need to go to extremely low values of $`1/\nu `$ $`(1/\nu 0.1)`$ in order to determine the ultimate fate of the extended states as $`B`$ 0.

This work was funded by the ARC. CEY acknowledges support from the IPRS scheme; MYS acknowledges an ARC/QEII Fellowship.


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# Untitled Document

Non-local Quantum Electrodynamics. II. Possibility of correlated $`2n`$-photon absorption

in gases leading to VERY High frequency spontaneous emission

and Very high order Harmonic Generation

Krishna Rai Dastidar† Department of Spectroscopy. Electronic address :spkrd@mahendra.iacs.res.in and T K Rai Dastidar**this work is dedicated to his memory

Indian Association for the Cultivation of Science, Calcutta 700 032, India

ABSTRACT

In a recent work  we expounded a non-local Quantum Electrodynamics (QED) which predicted a linear two-photon absorption by an atom placed in a laser field of appropriate intensity and frequency. In this paper we extend our earlier work to show that the theory allows for linear $`2n`$-photon absorption by gaseous matter where, under suitable conditions, $`n`$ may literally run upto thousands. The consequences of this extension of the theory are outlined and predictions are made which may be verified in laboratories.

I. INTRODUCTION

Recently  we showed that complex scalar fields remain covariant under a non-local Abelian gauge transformation, and showed how a non-local QED follows naturally from this gauge symmetry. (This paper will be referred to as I in the following.) The result can of course be trivially extended to spinor fields. From a practical point of view, the most important result of this nonlocal QED is that under suitable conditions that can be met in laboratory as well as cosmological environments, a two-photon absorption linear in intensity can occur from radiation fields travelling through gaseous matter. The impact of this new QED on atomic and molecular physics, particle physics and cosmology has been discussed in a series of papers \[1-4\]. In  we also suggested an experimental test for this abovementioned result.

In paper I, it has been shown  that the correlated two-photon absorption in atoms can give rise to probability which is linear in laser intensity. In this paper we will show that this correlated two-photon absorption process can be generalized to 2n-photon absorption process, where n can go upto thousands or more. Previously it has been shown that the correlated mode-pair of photons may exist under certain conditions, within the framework of non-local Quantum Electrodynamics (QED). By second quantization of this non-local field, correlated two-photon annihilation and creation operators were developed and it has been demonstrated that these operators operate on correlated photon number states by annihilating or creating two photons at a time respectively (one photon from each mode). Hence one can get correlated vacuum field in absence of any photons. Which means that the vacuum for the electromagnetic field is structured by the presence of this new type of non-local correlated zero-photon mode pairs. Here we will generalize this vacuum field by considering 2n correlated modes, where n can go upto a large number. But to make the zero point energy finite, one will have to put an upper limit to the value of n. The upper limit for the number n can be such that $`n\mathrm{}\omega m_ec^2`$ where $`m_e`$ is the rest mass of electron, c is the velocity of light and $`\omega `$ is the frequency of the photon.

It has been shown before that the correlated two-photon absorption can occur in a single electron or two-electron (preferably correlated) system, under the conditions that (i) the time for two-photon absorption $`\delta t<<\frac{1}{\omega }`$, where $`\omega `$ is the frequency of the photon and (ii) the number of photons (of energy flux I) passing through atomic volume V i.e. $`\frac{VI}{c\mathrm{}\omega }`$ must be greater than or equal to the number of outer-shell electrons ($`n_e`$) in the atom. Of course, above number of photons should be present within the volume V during the time $`\delta t`$, which is much less than $`\frac{1}{\omega }`$, so that the absorption can occur during this time interval. Therefore, there are three parameters V, I and $`\omega `$ which can be controlled to satisfy the condition

$$\frac{VI}{c\mathrm{}\omega ^2}>>n_e$$
$`(1)`$
For a single atom, V is fixed and if $`\omega `$ is given, one will have to increase the laser intensity I, so that the number of photons exceeds the number of electrons present in the outer shell. On the other hand if V can be made large as in the case of cluster of atoms, the condition (1) can be easily satisfied for a lower laser intensity. In case of n-photon absorption, where n can be large on the order of 1000, the cluster will be a preferable candidate, since it can have radius one or two orders of magnitude larger than the single atom. Under this condition absorption of 1000s’ of photons will be more efficient for clusters than for single atom for a given intensity of laser. Moreover, absorption of 1000s’ of photons in a single atom, within the interval of time $`\delta t`$ becomes a more stringent condition than that in cluster of atoms where a large number of electrons are available within the volume V.

In the previous paper it has been shown that the correlation among electrons may affect the phenomenon of correlated two-photon absorption by two-electron atoms. In this work we will not discuss about electron correlation, but it can be stated that the presence of electron correlation will also affect the $`2n`$ photon correlated absorption process.

Within the framework of non-local QED, the vacuum field is structured due to the presence of 2n correlated zero-photon modes and hence the electrons excited by 2n correlated photon absorption can spontaneuosly emit a single photon of energy $`2n\mathrm{}\omega _k`$ due to the interaction with this correlated vacuum field. This is the phenomenon which can be attributed to the emission of x-rays observed  in clusters when irradiated with strong lasers of intensity $`I10^{16}W/cm^2`$.

Application of the above formalism in the area of matter-radiation interaction has so far been confined to one- and two-electron atoms. In the present paper it will be shown that the abovementioned property of nonlocal gauge transformation symmetry can be extended in such a manner as to be directly applicable to $`n`$-electron systems, where $`n`$ can literally run upto thousands as for example in clusters. The results of the interaction of such systems with laser radiation can, according to this theory, be startling. One of the results that we are going to prove is the possibility of $`2n`$-photon absorption linear in intensity from a laser field, leading to the prospect of highly efficient $`2n`$-th order harmonic generation and/or spontaneous emission using gases consisting of $`n`$-electron atoms, molecules or clusters.

II. THEORY

We begin by giving a brief summary of the work presented in I.

For a wavefunction (or classical field) $`\varphi (x)`$ where $`x(𝐫,t)`$, one of the ways to ensure the covariance (i.e. form-invariance) of the Lagrangian under an Abelian gauge transformation (GT) of the second kind $`T=\mathrm{exp}(ie\mathrm{\Lambda }(x))`$ \[$`\mathrm{\Lambda }`$ being any arbitrary function of x\] is to replace the ordinary partial derivative $`_\mu /(x^\mu )`$ in the Lagrangian by a covariant derivative $`D_\mu `$ involving a dynamical field . $`D_\mu `$ is defined by the property that under the above GT, $`D_\mu \varphi `$ transforms in exactly the same manner as $`\varphi `$ does ; i.e. for infinitesimal $`\mathrm{\Lambda },\delta (D_\mu \varphi )=ie\mathrm{\Lambda }D_\mu \varphi `$. For a charged particle one can define $`D_\mu =_\mu +ieA_\mu (x)`$, where $`A_\mu =(A_0,𝐀)`$ is the electromagnetic field potential and $`e`$ plays the role of the coupling constant of the latter with $`\varphi (x)`$. To ensure covariance of $`D_\mu `$ under the above GT, the field potential $`A_\mu `$ should transform as $`A_\mu A_\mu +(_\mu \mathrm{\Lambda })`$. This, of course, agrees with the gauge arbitrariness of $`A_\mu `$ allowed by the gauge-independence of the electromagnetic field tensor $`F^{\mu \nu }=^\mu A^\nu ^\nu A^\mu `$.

Against this elementary background, we introduced in  a non-local gauge transformation $`𝒯=\mathrm{exp}(ie\mathrm{\Lambda }|xx^{}|)`$, whose action on $`\varphi `$ is defined by

$$𝒯\varphi \mathrm{exp}(ie\mathrm{\Lambda }(x,x^{}))\varphi (x^{})d^4x^{}$$
$`(1^{})`$
(A detailed discussion of this notation is given in , appendix A.) For a charged particle, this allows the construction of a new covariant derivative

$$𝒟_\mu =\frac{}{x^\mu }+\frac{}{x^\mu }+ie𝒜_\mu |xx^{}|$$

where the action of $`𝒟_\mu `$ on $`\varphi `$ is to be understood in the sense of eqn. (1’), and where the nonlocal $`𝒜`$ transforms as $`𝒜_\mu |xx^{}|𝒜_\mu |xx^{}|+_\mu \mathrm{\Lambda }|xx^{}|+_\mu ^{}\mathrm{\Lambda }|xx^{}|`$. The necessary and sufficient condition for gauge-independence of the corresponding nonlocal field tensor

$$^{\mu \nu }|xx^{}|=(^\mu +^\mu )𝒜^\nu |xx^{}|(^\nu +^\nu )𝒜^\mu |xx^{}|$$
$`(2)`$
is that the commutator $`[^\mu ,^\nu ]`$ should vanish, i.e. the non-locality of the field should be of the EPR-type.

Under the action of this nonlocal field $`𝒜`$, a typical matrix element of an atomic transition $`|i|f`$ is given by

$$M_{fi}(t)=\frac{e}{m}\psi _f(x),n_f|𝐩.𝒜(x,x^{})|\psi _i(x^{}),n_i$$
$`(3)`$
the integration running over $`d^3`$r and $`d^4x^{}`$. We have used the Coulomb gauge.

A Fourier expansion of this nonlocal potential can be carried out (see, e.g. ) via a double summation over the usual photon modes :

$$𝒜(x,x^{})=\underset{𝐤_1\lambda _1}{}\underset{𝐤_2\lambda _2}{}[C_{𝐤\lambda }\widehat{ϵ}_{𝐤\lambda }(\widehat{r},\widehat{r}^{})\mathrm{exp}(i𝐤_1.𝐫i\omega _{𝐤_1}t+i𝐤_2.𝐫^{}i\omega _{𝐤_2}t^{})+c.c.]$$
$`(4)`$
Using standard methods (see any textbook on QED) the energy of this nonlocal field in a volume $`\mathrm{\Omega }`$ is given by

$$W_2=\frac{1}{2}\underset{𝐤\lambda }{}(Y_{𝐤\lambda }^2+4\omega _𝐤^2Z_{𝐤\lambda }^2)$$
$`(5)`$
where $`Y_{𝐤\lambda }=i\frac{\sqrt{\mathrm{\Omega }/\pi }}{2c}2\omega _𝐤(C_{𝐤\lambda }C_{𝐤\lambda }^{}),Z_{𝐤\lambda }=\frac{\sqrt{\mathrm{\Omega }/\pi }}{2c}(C_{𝐤\lambda }+C_{𝐤\lambda }^{})`$. Each mode subscript $`𝐤\lambda `$ here actually stands for a phase-correlated mode pair $`(𝐤_1\lambda _1,𝐤_2\lambda _2)`$, and $`2\omega _𝐤`$ stands for $`\omega _{𝐤_1}+\omega _{𝐤_2}`$. The quantities $`Y`$ and $`Z`$ satisfy Hamilton’s canonical equations of motion with $`W_2`$ as the hamiltonian, and in I we quantized the nonlocal QED by requiring that $`Y`$ and $`Z`$ be $`q`$-numbers obeying the commutation relation

$$[Z_{𝐤\lambda },Y_{𝐤^{}\lambda ^{}}]=i\mathrm{}\delta _{\mathrm{𝐤𝐤}^{}}\delta _{\lambda \lambda ^{}}.$$

Ultimately, the nonlocal field energy comes out in terms of a new pair of creation and annihilation operators :

$$W_2=\frac{1}{2}\underset{𝐤\lambda }{}\mathrm{}\omega _𝐤(b_{𝐤\lambda }b_{𝐤\lambda }^{\mathrm{}}+b_{𝐤\lambda }^{\mathrm{}}b_{𝐤\lambda }),\mathrm{where}(b,b^{\mathrm{}})_{𝐤\lambda }=\frac{1}{\sqrt{2\mathrm{}\omega _𝐤}}(2\omega _𝐤Z_{𝐤\lambda }\pm iY_{𝐤\lambda })$$

Here $`b`$ and $`b^{\mathrm{}}`$ are two-photon annihilation and creation operators, obeying the new commutation relations :

$$[b_{𝐤\lambda },b_{𝐤^{}\lambda ^{}}^{\mathrm{}}]=2\delta _{\mathrm{𝐤𝐤}^{}}\delta _{\lambda \lambda ^{}},[b_{𝐤\lambda },b_{𝐤^{}\lambda ^{}}]=[b_{𝐤\lambda }^{\mathrm{}},b_{𝐤^{}\lambda ^{}}^{\mathrm{}}]=0$$

A natural extension of the non-local GT (1) to the case of a two-particle system would be the transformation $`𝒯_2|x_1,x_2x_1^{},x_2^{}|`$ which, written out in full, becomes

$$𝒯_2\varphi (x_1,x_2)\mathrm{exp}(ie\mathrm{\Lambda }(x_1,x_2,x_1^{},x_2^{}))\varphi (x_1^{},x_2^{})d^4x_1^{}d^4x_2^{}$$
$`(6)`$
This allows for a new covariant derivative

$$𝒟_{2\mu }=_{1\mu }+_{2\mu }+_{1\mu }^{}+_{2\mu }^{}+𝒜_{2\mu }|x_1,x_2x_1^{},x_2^{}|$$
$`(7)`$
whereupon the matrix element for the transition $`|i|f`$ becomes

$$M_{2_{fi}}(t)=\frac{e}{m}\psi _f(x_1,x_2),n_f|(𝐩_1+𝐩_2).𝒜_2(x_1,x_2,x_1^{},x_2^{})|\psi _i(x_1^{},x_2^{}),n_i$$
$`(8)`$
Let us now extend this formalism to correlated 2n-photon absorption in a n-electron system, by using the fourier expansion  of non-local vector potential as follows:

$$𝒜(x_1,,x_n,x_1^{},,x_n^{})=\underset{𝐤_1\lambda _1}{}\underset{𝐤_n^{}\lambda _n^{}}{}[C_{𝐤\lambda }\widehat{ϵ}_{𝐤\lambda }(\widehat{r}_1,,\widehat{r}_n,\widehat{r}_1^{},\widehat{r}_n^{})$$

$$\mathrm{exp}(i𝐤_1.𝐫_1++i𝐤_n.𝐫_ni\omega _{𝐤_1}t_1i\omega _{𝐤_n}t_n)$$

$$X\mathrm{exp}(i𝐤_1^{}.𝐫_1^{}++i𝐤_n^{}.𝐫_n^{}i\omega _{𝐤_1}^{}t_{}^{}{}_{1}{}^{}i\omega _{𝐤_n}^{}t_{}^{}{}_{n}{}^{})+c.c]$$
$`(9)`$
Each mode subscript $`𝐤\lambda `$ here actually stands for n phase-correlated mode pairs$`(𝐤_1\lambda _1,𝐤_1^{}\lambda _{1}^{}{}_{}{}^{}),,(𝐤_n\lambda _n,𝐤_n^{}\lambda _{n}^{}{}_{}{}^{})`$.

Hence the electric field amplitude $`(x_1,,x_n,x_1^{},,x_n^{})`$ can be obtained by evaluating the time derivatives of A with respect to times $`t_1,t_n^{}`$. By using the usual method one can obtain the field energy density in terms of new c-numbers $`Y_{N𝐤\lambda }`$ and $`Z_{N𝐤\lambda }`$ where

$$Y_{N𝐤\lambda }=i\frac{\sqrt{\mathrm{\Omega }/\pi }}{2c}N\omega _𝐤(C_{𝐤\lambda }C_{𝐤\lambda }^{})$$

,

$$Z_{N𝐤\lambda }=\frac{\sqrt{\mathrm{\Omega }/\pi }}{2c}(C_{𝐤\lambda }+C_{𝐤\lambda }^{})$$

. Here $`N\omega _𝐤`$ stands for $`\omega _{𝐤_1}++\omega _{𝐤_n}^{}`$. The quantities $`Y`$ and $`Z`$ satisfy Hamilton’s canonical equations of motion with the total field energy as the hamiltonian. To second quantize the nonlocal QED, $`Y`$ and $`Z`$ are considered to be $`q`$-numbers obeying the commutation relation

$$[Z_{N𝐤\lambda },Y_{N𝐤^{}\lambda ^{}}]=i\mathrm{}\delta _{\mathrm{𝐤𝐤}^{}}\delta _{\lambda \lambda ^{}}.$$

Ultimately, the field energy can be written in terms of a new pair of creation and annihilation operators defined as

$$(b_N,b_N^{\mathrm{}})_{𝐤\lambda }=\frac{1}{\sqrt{2\mathrm{}\omega _k}}N\omega _𝐤(Z_{N𝐤\lambda }\pm iY_{N𝐤\lambda })$$
$`(10)`$
these operators obey the commutation relations as follows

$$[(b_N)_{𝐤\lambda },(b_{}^{\mathrm{}}{}_{N}{}^{})_{𝐤^{}\lambda ^{}}]=N\delta _{\mathrm{𝐤𝐤}^{}}\delta _{\lambda \lambda ^{}},[(b_N)_{𝐤\lambda },(b_N)_{𝐤^{}\lambda ^{}}]=[(b_N^{\mathrm{}})_{𝐤\lambda },(b_N^{\mathrm{}})_{𝐤^{}\lambda ^{}}]=0$$

These annihilation and creation operators operate on the correlated phopton number states as annihilating N number of photons or creating N muber of photons respectively as follows:

$$(b_N)_{𝐤\lambda }|n_{𝐤\lambda }=\sqrt{n}_{𝐤\lambda }|n_{𝐤\lambda }N$$

and

$$(b_N^{\mathrm{}})_{𝐤\lambda }|n_{𝐤\lambda }=\sqrt{n_{𝐤_\lambda }+N}|n_{𝐤\lambda }+N$$
$`(11)`$
Therefore $`(b_N)_{𝐤\lambda }`$ and $`(b_{}^{\mathrm{}}{}_{N}{}^{})_{𝐤\lambda }`$ are the N-photon annihilation and creation operators respectively. Hence the vector potential and the field amplitude can be expressed in terms of these operators as shown in paper I. Therefore the dipole transition matrix elements for correlated 2n-photon absorption by n electrons (such as in clusters) can be given as:

$$𝒳_{Nfi}=\frac{\sqrt{2\pi I}}{c}\psi _{l_f,}(𝐫_1,𝐫_n)|(𝐫_1++𝐫_n)$$

$$.\widehat{ϵ}_{N𝐤\lambda }(\widehat{r}_1,,\widehat{r}_{}^{}{}_{n}{}^{})|\psi _{l_i}(𝐫_1^{},𝐫_n^{})$$
$`(12)`$
where the polarization vector $`\widehat{ϵ}_{N𝐤\lambda }`$ can be expressed as

$$\widehat{ϵ}_{𝐤\lambda }(\widehat{r}_1,,\widehat{r}_n,\widehat{r}_{}^{}{}_{1}{}^{},,\widehat{r}_n^{})=\underset{j}{}a_j\mathrm{\Pi }_i(\widehat{r}_i+\widehat{r}_{}^{}{}_{i}{}^{})P_j(\widehat{r}_i.\widehat{r}_{}^{}{}_{i}{}^{})$$

where j varies from 0 to $`\mathrm{}`$ and $`i=1,2,n`$ Mod square of the matrix element $`𝒳_{Nfi}`$ will give rise to N-photon absorption probability which varies linearly with laser intensity. One can get the selection rule for the angular momentum by considering the angular integrals (as shown in paper I) as $`l_f=l_i`$ and $`l_f=l_i+N`$

III. DISCUSSIONS

It has been shown before, that the non-local theory has wide applications \[1-4\] in the fields of atomic/molecular physics, cosmology and particle physics. Recently it has been applied to explain the phenomenon of direct double ionization in atoms  in intense laser fields. Here it has been shown that the non-local model of QED can also be applied to explain the emission of x-rays from cluster of atoms when irradiated with strong laser field of intensity $`>10^{16}W/cm^2`$. In cluster of atoms the radius of the cluster can be 10 times larger than that of a single atom and hence the volume can be $`10^3`$ times larger than that of a single atom. It is obvious that the intensity (I) for correlated 2n-photon excitation can be atleast three orders of magnitude less than that required for the single atom (consider the relation (1)), in particular for a large number (can be 1000 or more) of photon absorption. Therefore the efficiency of emission will increase with the increase in the size of the clusters. But there is a limit in the increase of the size of clusters, since for efficient absorption the condition (1) should be satisfied. Increase in the size of the cluster means addition of more atoms and hence increase in the available number of electrons ($`n_e`$). Therefore if the increase in $`n_e`$ is faster than the increase in $`V`$, the condition (1) fails to be satisfied. Moreover emission from clusters of high-Z atoms will be more effective, since in that case the available number of electrons will be more for the same size of the the ciuster of low-Z atoms. Furthermore, there exists a cutoff intensity below which x-ray emission from a cluster cannot be obtained (see quation (1)). For x-ray emission in a particular region of wavelength, the cutoff intensity will be different for clusters of different atoms. According to this theory, since the 2n-photon correlated absorption should occur during a very short time $`<<\frac{1}{\omega }`$, this phenomenon will be more effective for short-pulsed lasers. Some of the above mentioned features have already been observed in recent experiments  on x-ray emission from clusters of different atoms in presence of strong laser fields. Moreover in recent experiments  it has been found that together with the sharp higher order harmonic generations, x-ray emissions of relatively broad spectrum occur and persist for a long time. It has been shown above that once the atoms in cluster are excited by the absorption of correlated 2n-photons, can emit spontaneously (photons of energy around $`2n\mathrm{}\omega `$) due to the interaction of the excited atom/highly charged ions with the vacuum of correlated modes. Since the duration of spontaneous emission depends on the natural linewidth of the states from which it is emitted, it can be as long as few nanoseconds . Let us consider a situation under which spontaneous emission of duration 1 nanosecond can occur from a highly excited atom/highly charged ion. If the duration of spontaneous emission of $`12ev`$ photon can be of the order of 100 ns (e.g. spontaneous emission from $`B^1\mathrm{\Sigma }_u`$ state to the ground state of $`H_2`$ molecule), then for $`1200ev`$ photon the duration of spontaneous emission can be of the order of 1 nanosecond, if the dipole transition moment from the ground state of the atom to the highly excited state is less in magnitude by two orders from that of $`H_2`$ molecules (between the first excited state and the ground state). Hence it is likely that the spontaneous emission from clusters can persist for 1 or two nanoseconds. Another possibility is that the innershell ionization of atoms in clusters can occur due to the highly efficient correlated 2n-photon absorption, followed by x-ray emission.

The wavelength dependence of x-ray emission from cluster has been observed to be more efficient for shorter wavelength lasers (248 nm) than that for the longer one (800 nm). This may be due to the fact that for long wavelength lasers the number of photons required for a particular transition is much larger than that for short wavelength lasers. Therefore it will lead to higher order transitions and hence correlation may be destroyed during the process of absorption.

Most striking feature of this type of absorption in the non-local picture of the electromagnetic field is that in this correlated 2n-photon absorption process, the probability for absorption varies linearly with laser intensity, thus making the absorption process much more efficient than that for multiphoton transition in the local picture of the electromagnetic field. Therefore within the framwework of non-local QED, the 2n-photon correlated absorption and hence the spontaneous emission/ higher order harmonic generation from the cluster will be very much effective in presence of very strong laser ($`I>10^{16}W/cm^2`$) field.

Moreover in the field of interaction of matter with radiation, one can predict that if the 2n-photon correlated absorption of radiation by the electrons in matter is feasible (in this model of non-local QED), leading to processes such as pair production, the phenomenon of pair production will be visible for much lower intensity than that required for conventional transitions.

In conclusion, it has been shown that the two-photon correlated absoption model in the non-local QED can be extended to any arbitrary 2n-photon correlated absorption and hence leading to efficient harmonic generation and/or spontaneous emission due to the interaction with structured vacuum ( of correlated modes). This type of absorption can occur in cluster of atoms when irradiated with short-pulsed intense radiation field and the efficiency of this process will be much greater than the conventional multiphoton processes, since the 2n-photon absorption in the non-local model is linearly dependent on laser intensity. With this model of non-local QED, some experimentally observed features could be explained and some predictions have been made which can be verified in the laboratory.

ACKNOWLEDGEMENT

K.R.D. is thankful to Prof. J. P. Connerade for helpful discussions.

REFERENCES

 T K Rai Dastidar and K Rai Dastidar, Mod.Phys.Lett. A13, 1265 (1998), Errata A13, 2265 (1998) ; hep-th/9902020

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 Introduction of a dynamical field is a sufficient but not a necessary condition for constructing a covariant derivative ; a pure gauge field, which may be taken to the limit $`0^+`$, can be used as well. See T K Rai Dastidar and K Rai Dastidar, Nuovo Cimento 109B, 1115 (1994) ; Mod. Phys. Lett. A10, 1843 (1995). The most important finding of these papers was that, contrary to conventional wisdom, free-particle equations of motion in both non-relativistic as well as relativistic Quantum Mechanics are covariant under Abelian gauge transformations of the second kind.

 I M Gelfand and G E Shilov, Generalised Functions (Academic Press, 1964) Vol. I, Chap. 2, Eq. (1.3)(1)

 T. Ditmire, T. Donnelly, A.M. Rubenchik, R.W. Falcon and M.D. Perry, Phys. Rev. A, 53, 3379 (1996); H. Honda, E. Miura, K. Karsura, E. Takabashi and K. Kondo, Phys. Rev. A, 61, 023201 (2000)

 K. Rai Dastidar (communicated)