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# Temperature-induced barium de-trapping from a double-well potential in Ba6Ge25

## I Introduction

There is growing interest in open-structure semiconducting materials that are considered promising candidates for thermoelectric applications. These compounds are characterized by low and often glass-like thermal conductivity $`\kappa `$, high electric conductivity $`\sigma `$ and large Seebeck coefficient $`S`$. In particular, a significant research effort has focused on group III and IV clathrates, with heavy alkali metal, alkaline earth or rare earth guests. The group III and IV elements form a network of cages, in which a large atom is hosted. Usually, the guest atom is weakly bonded to the cage Blake et al. (2001) and the sizes of cages are large enough for the atom to rattle. The semiconducting host can be doped to provide suitable electronic properties while the heavy guest atom can significantly lower the thermal conductivity of the material, due to resonant scattering of the heat carrying phonons Nolas et al. (2000); Sales et al. (2001); Keppens et al. (2000), thereby increasing the thermoelectric figure of merit $`Z=S^2\sigma /\kappa `$. These materials are a realization of the “phonon glass, electron crystal” (PGEC) model proposed by Slack Slack (1995).

The best-known materials of this class, such as (Ba, Sr, Eu)8Ga16Ge30, adopt the so-called type-I clahtrate structure, which is also common to a variety of gas hydrates Pauling and Marsh (1952); Sales et al. (2001); Nolas et al. (2000), and contains highly symmetric dodecahedral and tetrakaidecahedral cages Chakoumakos et al. (2000); Sales et al. (2001). Ba6Ge25 is also a member of the clathrate family, but its crystal structure and its behaviour are unusual. Ba6Ge25 crystallizes in the cubic P $`4_1`$ 3 2 space group with a lattice parameter $`a=14.54536(7)`$ Å and $`Z=4`$. Barium occupies three non-equivalent crystallographic positions in the Ba6Ge25 unit cell Carrillo-Cabrera et al. (2000); Fukuoka et al. (2000); Kim et al. (2000). Ba(1) (8 equivalent sites per unit cell) is contained in distorted dodecahedral cages, sharing the pentagonal faces with each other and forms a spiral structure across the unit cell. However, Ba(2) (4 per unit cell) and Ba(3) (12 per unit cell) are hosted in channel-like structures that are interconnected throughout the unit cell Carrillo-Cabrera et al. (2000); Fukuoka et al. (2000); Kim et al. (2000). Another unusual structural feature is the fact that 32 out of 100 Ge atoms in each unit cell are three-coordinated, and accommodate a lone electron Carrillo-Cabrera et al. (2000); Fukuoka et al. (2000); Kim et al. (2000). The transport and magnetic properties of Ba6Ge25 are also unusual. Unlike (Ba, Sr, Eu)8Ga16Ge30, which can be prepared in both semiconducting and metallic form by slightly altering the Ga/Ge ratio, Ba6Ge25 is an $`n`$-type metal, with a fairly high carrier concentration ($`n`$1– 2$`10^{22}`$cm-3), and a good room-temperature electrical conductivity ($`2000\mathrm{\Omega }^1`$cm-1) Kim et al. (2000); Paschen et al. (2002). The room-temperature Seebeck coefficient (-20 $`\mu `$V/K) is also consistent with metallic rather than semiconducting properties. Upon cooling below 240 K, Ba6Ge25 undergoes a transition, affecting the electrical conductivity (which decreases by almost a factor of 4), the Seebeck coefficient (which is negative and increases in absolute value) and the magnetic susceptibility $`\chi `$, (which becomes more diamagnetic) Paschen et al. (2002). At low temperatures, Ba6Ge25 is still a metal, as clearly indicated by the linear temperature dependence of the specific heat and Seebeck coefficient, and by the high carrier density, as determined by Hall effect measurements Kim et al. (2000); Paschen et al. (2002). Moreover, a superconducting transition has been discovered below 1 K Grosche et al. (2001).

This intriguing behaviour is clearly very difficult to understand with the naive Sommerfeld approach. In the free-electron model Ashcroft and Mermin (1976), $`\sigma `$ , $`S`$ and the electronic (Pauli) component of the magnetic susceptibility $`\chi _e`$ are proportional to $`n`$, $`n\pm 2/3`$ and $`n+1/3`$, respectively. $`\sigma `$ is also proportional to the relaxation time $`\tau `$, whereas the other two quantities are independent of $`\tau `$. Qualitatively, one may conclude from the sign of the anomalies that a sharp reduction of the carrier concentration is occurring on cooling below the transition. However, recent Hall effect and specific heat measurements by Paschen et al. Paschen et al. (2002); Steglich et al. (2002) indicate that this is not the case. In fact, if the Hall measurements are interpreted in the simple single-band model, the drop in conductivity is almost entirely accounted for by a simultaneous drop in carrier mobility (which is proportional to $`\tau `$). The interest in this compound has been further heightened by a report of a structural transition at the same temperature where the transport and magnetic anomalies occur. Although the crystallographic data are still unpublished, they are discussed in the aforementioned work by Paschen et al. Paschen et al. (2002) and used by Zerec et al. Zerec et al. (2002) to calculate the electronic band structure of , Ba6Ge25. The structural anomaly is not accompanied by a symmetry reduction. It is due to a strong increase of the Ba site disorder on cooling, and is consistent with the Ba atoms ’locking in’ to two well-separated positions (split sites) at low temperatures. Paschen et al. speculate that the unusual transport and magnetic properties of Ba6Ge25 may arise from the formation of spinless bipolarons, whereby two carriers with opposite spins would dynamically stabilize a pair of Ba atoms separated by a short nearest-neighbour distance. Clearly, such a scenario may have important implications for understanding superconductivity in this system.

In this paper, we present detailed temperature dependent measurements of the Ba6Ge25 clathrate crystal structure, as determined from Rietveld refinements of neutron powder diffraction data in the temperature range 20– 300K. The scattering contrast of Ge and Ba for neutrons (bBa=3.86 fm; bGe=8.18 fm) is reversed with respect to x-rays (ZBa=56; ZGe=32), providing a unique perspective not only on the large barium displacements, but also on the smaller displacements of the germanium framework. We conclude that, at low temperatures, Ba(2) and Ba(3) are trapped in a deep double-well potential, and that dynamic displacement coupled with electron hopping is very unlikely to occur. The trapping of barium atoms results in a dramatic structural rearrangement, which is bound to have a profound influence to the electronic states near the Fermi energy, especially those associated with narrow bands with predominant Ba character. Under these circumstances, the free- electron interpretation of the transport and magnetic properties clearly breaks down. However, we find that the single-electron (band) picture in the semi- classical approximation is most likely sufficient to describe this system, without any need to invoke exotic electron-electron interaction mechanisms.

## II Experimental

Polycrystalline Ba6Ge25 was prepared from elemental barium (99.2% purity, from Alfa Aesar) and germanium (99.999% purity, from Alfa Aesar) mixed together in the molar ratio of $`1.15:4`$. Excess Ba was added to compensate for its evaporation from the reaction vessel. The mixture was placed in a closed graphite crucible, which was sealed in an evacuated silica ampoule. The reactants were slowly heated up to 1353K over a period of 10h and kept at this temperature for 8h. Then the sample was cooled down to room temperature over a period of 10h. The resulting sinter was black with brown tarnish layer on the surface. The brown impurity was washed away using methanol in an ultrasonic cleaner. The material was found to contain traces of graphite from the reaction crucible, as well as small traces of an unidentified phase. Neutron diffraction patterns were collected using the General Materials Diffractometer (GEM) at Rutherford Appleton Laboratory. The sample for the scattering experiment was enclosed in a vanadium can and attached to a closed cycle helium refrigerator. The measurements were carried out in the temperature range of 20–300K with 10K increments. At every temperature, data was acquired for 1h at 175 $`\mu `$A of proton beam current. The Rietveld analysis of the diffraction patterns was carried out using the GSAS package Larson and von Dreele (2000). The crystal structure was visualized using ORTEP-3 program Farrugia (1997).

## III Structure properties

Ba6Ge25 was found to be cubic (space group P $`4_1`$ 3 2) in the entire temperature range, with no trace of additional Bragg peaks at low temperatures. Preliminary Rietveld refinements were carried out using a model derived from room temperature x-ray single crystal experiments Fukuoka et al. (2000); Carrillo-Cabrera et al. (2000); Kim et al. (2000). In this paper we follow the atom labelling scheme of Kim et al. Kim et al. (2000).

Fig. 1 shows the $`a`$ lattice parameter of Ba6Ge25 as a function of temperature. The lattice parameter increases with increasing temperature, but exhibits an anomaly in the 200–240K temperature range which indicates the phase transition in Ba6Ge25, as reported by Paschen et al. Paschen et al. (2002). The overall lattice expansion of Ba6Ge25 is $`\mathrm{\Delta }a=0.018`$Å ($`\mathrm{\Delta }a/a0.1`$%) in the 20–300K temperature range. It should also be noted that the lattice parameter contraction associated with the anomaly is very small (0.004Å). In our data the contraction happens smoothly over a 40 K range. This smooth cross-over is also reflected in our measurements of resistivity (see inset in Fig. 1) and contrasts with the sharp cross-over reported by Paschen et al. Paschen et al. (2002). These authors report a transition with first-order character, accompanied by hysteresis.

The atomic displacement parameters (ADP’s) of Ba(2) and Ba(3) at room temperature were found to be large and anisotropic as previously reported Fukuoka et al. (2000); Kim et al. (2000). A refinement of the low temperature patterns produced even larger displacements, increasing with decreasing temperature. This behaviour clearly indicated that the room temperature model is not adequate for the low temperature structure. The Ba(2) and Ba(3) sites were examined using difference Fourier maps. The maps present the difference between the experimental data and the model with an empty Ba site. The results for 20K, 200K, 240K and 300K are presented in Fig. 2. The low temperature nuclear density distribution maps (20K) clearly show the tendency of Ba(2) and Ba(3) atoms to move away from the site centre. This effect is especially pronounced in the case of the Ba(3) site. The site separation increases with decreasing temperature. Inspection of the maps shows that the splitting of the Ba(2) site virtually disappears above 240K but the Ba(3) site still shows signs of the site separation up to 300K. Multiple rattler sites were observed in Sr and Eu bearing type-I clathrates (X8Ga16Ge30) but not in the Ba isomorph Chakoumakos et al. (2000); Sales et al. (2001); Nolas et al. (2000); Keppens et al. (2000). This effect was accommodated in the current model by splitting the Ba(2) and Ba(3) sites along the direction of the largest thermal displacement at all temperatures. The symmetry of the Ba sites was reduced as follows: Ba(2) 4a $``$ 8c; Ba(3) 12b $``$ 24e. The split Ba site occupancies were reduced to 0.5 to maintain the overall stoichiometry. Using this model the refinement produced sensible thermal displacement of Ba atoms. At room temperature, the two models are almost equivalent, but, for consistency, we chose to carry out all the refinements using the split-site model. Sets of refined atomic coordinates and Debye-Waller factors at 20K and 300K are presented in Tables 1-2. An example of a refined pattern is shown in Fig. 3.

## IV Bond geometry

As the Ba6Ge25 crystal structure is complex, its analysis becomes easier by focusing on the Ge framework and on its individual building blocks (cages), bearing in mind that the cages share faces with each other and changes to a single Ge-Ge bond length affects all the cages. As already mentioned, the case of Ba6Ge25 is unusual as the movement of Ba atoms also affects the Ge framework.

### IV.1 Ge framework

All Ge-Ge bonds in the Ba6Ge25 structure are longer than in the elemental Ge (2.45Å). The Ge(1)-Ge(5) (equal to 2.48Å and 2.54Å) and Ge(4)-Ge(4)=2.47Å (the latter belongs to Ba(3) cage discussed below) distances are constant with temperature and are the shortest in the Ge network. All other Ge-Ge bonds with the exception of Ge(2)-Ge(3) and Ge(1)-Ge(6) monotonically increase with temperature within the range 2.535–2.615Å as expected from thermal expansion. The Ge(2)-Ge(3) and Ge(1)-Ge(6) bond lengths are presented in Fig. 4 as functions of temperature. These bonds are almost constant below 100K and above 250K and change between 100K and 250K, with maximum derivative in the 200–240K temperature range, corresponding to the magnetic and transport anomalies Paschen et al. (2002). The transition also leads to small (less than one degree) changes in Ge-Ge-Ge angles associated with three-coordinated germaniums.

### IV.2 Ba(1) cage

The local environment of Ba(1) is presented in Fig. 5. Ba(1) is contained in a distorted dodecahedral cage with a 3-fold symmetry axis. Ba(1) cages share the pentagonal faces with other Ba(1) and Ba(3) cages and form a spiral structure in the crystal. Ba(1) together with Ge(4) and Ge(6) are located on the 3-fold axis, which is also the direction of their largest thermal displacement. The Ba(1)-Ba(1) nearest neighbour distance increases with temperature from 5.43Å at 20K to 5.46Å at 300K and does not show any signs of transition. The shortest Ba(1)- Ge(2)$`3.5`$Å and Ba(1)-Ge(5)$`3.4`$Å bonds are constant with temperature and the Ba(1)-Ge(1) shortest distance increase with temperature from 3.42Å at 20K to 3.46Å at 300K. These are the shortest Ba(1)-Ge bonds in the Ba(1) cage. Their value suggests that Ge(1), Ge(2) and Ge(5) are at contact distance from Ba(1). The environment of Ba(1) seems to be the same as in the type-I clathrates (the lengths are the same as calculated for Ba8Ga16Ge30 cages) Blake et al. (2001). The remaining Ba(1)-Ge bonds change with temperature within the range 3.470–3.935Å.

The reduction of Ge(2)-Ge(3) distance described above leads to a step like reduction of the Ba(1)-Ge(3) and Ba(1)-Ge(4) distances, as shown in Fig. 6. The increase of the Ge(1)-Ge(6) bond causes the Ge(6) atom to move away from Ba(1) (see Fig. 6). However, the Ba(1)-Ge(6) increase is greater than Ba(1)-Ge(4) decrease so the entire Ba(1) cage expands along 3-fold axis by 0.03Å over the 20–300K temperature range. The length of the Ba(1) cage along the 3-fold axis is presented in Fig. 7 as a function of temperature.

### IV.3 Ba(2) cage

The Ge(3) and Ge(6) atoms form a pseudo-cubic environment of Ba(2) presented in Fig. 5. Ge(6) and Ba(2) lie on the 3-fold axis of the unit cell and triplets of Ge(3) atoms on both sides of Ba(2) form equilateral triangles rotated almost 60 with respect to each other. Each Ba(2) cage is connected to six Ba(3) cages and together form channels in the crystal structure. It should be noted that only one of the split Ba sites is occupied at a time. On average, each of the wells is occupied with 50% probability. From our data, no long-range correlation between occupied sites can be detected, since no superlattice Bragg reflections are observed at low temperatures. However, the possibility of short-range ordering, leading, for example, to the formation of clusters of Ba2+ ions, could not be ruled out. This aspect is currently being investigated by means of diffraction techniques that are sensitive to the local structure.

The distance between the split Ba(2) sites is presented in Fig. 8 as a function of temperature. The separation of Ba atoms is constant up to 100K then starts to decrease and rapidly falls in the 200–250K range. This sudden decrease in the Ba(2)-Ba(2) site distance coincides with the kink in the lattice parameter (see Fig. 1). The shape of this curve closely follows the shape of the Ba6Ge25 resistivity curve of Paschen et al. Paschen et al. (2002). At room temperature the split Ba(2) sites remain separated by 0.4Å.

The Ba(2)-Ge(3) bonds, marked with solid lines in Fig. 5, are constant up to 200K ($``$3.31Å) and increase to 3.34Å in the 200– 250K temperature range. The almost constant value of the distance suggests a bonding of the three-coordinated Ge(3) with Ba(2) or a close contact of both atoms. These lengths are characteristic for Ba-Ge bonds observed in other Ba-Ge intermetallics Turban and Schaefer (1973); Evers et al. (1980); Vaughey et al. (1997); Kroener et al. (1998); Zuercher and Nesper (1998). The Ba(2)-Ge(6) distance is too large ($`>3.6`$Å) for Ge(6) to form a bond with Ba(2). The length of the Ba(2) cage along the 3-fold axis is presented in Fig. 7 as a function of temperature. Its size decreases by $`0.06`$Å at the phase transition.

### IV.4 Ba(3) cage

The Ba(3) atom is contained in a heavily distorted dodecahedral cage presented in Fig. 9. This cage is the largest in the Ba6Ge25 structure and has 2- fold symmetry with the rotation axis bisecting the Ge(1)-Ge(1) and Ge(4)-Ge(4) bonds. As in the case of Ba(2) cage, only one of the split Ba sites is occupied ; the distance between the split sites is shown in Fig. 8 as a function of temperature. The Ba(3) site separation exhibits similar behaviour to the Ba(2) site in the same temperature region. However the room temperature separation distance is equal to 0.56Å. Fig. 10 shows the Ba(2) site separation as a function of the Ba(3) site separation. The displacement amplitudes of Ba atoms in both cages are clearly correlated. However, the straight line fitted to the data does not cross the origin of the plot. Its negative offset indicates that Ba(3) atom can still be displaced from the cage centre while Ba(2) atom remains in the centre of its cage. This is consistent with the Fourier maps presented in Fig. 2.

The shortest Ba(3)-Ge distances are again formed by three coordinated Ge(3) and Ge(6) atoms. The Ba(3)-Ge(3)$`3.3`$Å and Ba(3)-Ge(6)$`3.43`$Å distances are constant. The remaining Ba(3)-Ge bonds are greater than 3.45Å and vary with temperature. Once again, this suggests close contact of Ba and Ge atoms.

As indicated above the split site model yields acceptable temperature dependence of Ba thermal parameters, see Table 2. The thermal displacement of Ba(2) and Ba(3) is the largest among all atoms and their temperature dependence shows signs of the transition. This is most likely due to contraction of the Ge host in the 200–240K temperature range, which constricts the thermal movement of the rattlers. Also Ge(6) exhibits a substantial but constant thermal displacement along the 3-fold axis. This 3-coordinated Ge atom exhibits large thermal displacement because of the geometry of the lattice. Ge(6) is coordinated to three Ge(1) atoms but large distance to Ba(1) and Ba(2) along the 3-fold axis (see discussion above) allow it to move freely.

### IV.5 Concluding remarks

The introduction of the split sites in Ba(2) and Ba(3) cages leads to a minimum Ba(2)-Ba(3) distance. The shortest distance between Ba(2) and Ba(3) is presented in Fig. 11 as a function of temperature. The Ba(2)-Ba(3) closest distance is of the same order as in the elemental Ba (4.35Å). It seems that Ba atoms can interact with each other, which is consistent with theoretical predictions Blake et al. (2001).

## V Discussion and conclusions

The results of the previous sections can be summarised as follows: we have observed clear changes in both lattice and internal structural parameters, associated with the well-known anomalies in the transport and magnetic properties of Ba6Ge25. The most remarkable structural change is the displacement of Ba(2) and Ba(3) away from their high-symmetry site, thereby forming a two-fold split site occupied in a random way with 50% probability. This splitting may already be present at room temperature, but is greatly enhanced on cooling, with a sudden increase through the transition. We have also evidenced significant changes in the Ge framework at the transition. Interestingly, the most significant framework distortions affect the position of Ge(3) and Ge(6) (through the Ge(2)-Ge(3) and Ge(1)-Ge(6) bond lengths and associated bond angles). Ge(3) and Ge(6) are both 3-coordinated and both form close-contact distances with Ba(2) and Ba(3). Based on this scenario, we will attempt to relate the observed structural changes to the known anomalies in the transport and magnetic properties; in particular, we will focus on three main questions: 1) What is the driving force for the Ba-site splitting on cooling? 2) What is the likely effect of this distortion on the electronic structure, and is this sufficient to explain the observed anomalies? 3) Is there any need to go beyond the one-electron approximation? Question number 3 is particularly relevant in the light of the spinless bipolaron mechanism proposed by Paschen et al. Paschen et al. (2002) to explain the drop in magnetic susceptibility, and of the observation of superconductivity in this system below 1 K Grosche et al. (2001).

### V.1 Mechanism of the structural transition

The simplest mechanism for explaining the observed behaviour of the Ba(2) and Ba(3) sites is that of temperature-induced de-trapping from a symmetric double- well potential; this is a purely ’geometrical’ effect, which would take place within a rigid framework and, in its simplest form, does not depend on the conduction electrons. In this case, the close-contact interaction between Ba and the 3-fold-coordinated Ge atomes (Ge(3) and Ge(6) would provide both the attractive and the repulsive components of the potential. A quartic potential bounded on both sides by infinite walls provides the simplest implementation of this model (Fig. 12), which can be solved numerically in both classic and quantum cases. Qualitatively, the physics of this model is easy to understand and is in agreement with the observations: at low temperatures, Ba(2) and Ba(3) are statistically trapped in one of the two wells of a symmetric double-well potential. On warming, the atoms explore the available levels within each well, but remain confined until their energy becomes comparable with that of the central maximum. When the thermal energy becomes comparable to the barrier height, the atoms are ’de-trapped’, and become free to jump between wells and to occupy the central position with finite probability. Quantitatively, the quartic potential model is able to explain only about 30% of the change in Ba-Ba split distances, but larger changes can be obtained by using more realistic potentials Radaelli . Irrespectively of the details of the potential, the main drawback of this model is that it only produces smooth crossovers through the de-trapping temperature, and is therefore unable to describe a first-order transition as observed by Paschen et al. Paschen et al. (2002). However, we have clearly shown that the Ge framework distorts in a significant way through the transition, and it is conceivable that the Ba- Ge interaction could modify the character of the transition. In spite of these difficulties, we are persuaded that the key to understand the structural transition is the formation of symmetric double-well potential at the Ba(2) and Ba(3) sites. The role of frustration in preventing a collective structural distortion also deserves to be investigated.

### V.2 Consequence of the structural transition on the electronic structure

At low temperature the Ba(2) and Ba(3) ions are displaced; however, no superlattice peaks are evident therefore the displaced sites must be occupied in a random, or short-range ordered, fashion. We would like to examine the possible effect of this on the electronic and transport properties. We have shown that structural changes occur for both the Ba sites and the Ge framework, strongly suggesting that the disorder will result in increased scattering for bands with both Ba and Ge predominant character. This observation, by itself, is sufficient to explain the drop of carrier mobility on cooling, which would be a consequence of the reduced mean free path for the conduction electrons. However, the observation of anomalies in both the Seebeck coefficient and the magnetic susceptibility clearly indicate that changes in the electronic structure at the Fermi surface are taking place through the transition. If we abandon the naive free-electron model and write $`S`$ and $`\chi _e`$ in the semiclassical one-electron model Ashcroft and Mermin (1976) we obtain:
$`S=\frac{\pi ^2}{3}\left(\frac{k_B}{e}\right)k_BT\frac{\mathrm{log}\sigma (E)}{E}|_{E_F}`$,
$`\chi _{Pauli}=\mu _B^2g(E_F)`$
where $`\sigma (E)=e^2\tau (E)g(E)\frac{1}{3}v(E)^2`$ is the generalised conductivity, $`\tau (E)`$ is the relaxation time, $`g(E)`$ is the density of states (DOS) and $`v(E)`$ is the electron velocity (which we considered isotropic for simplicity; all terms are formally energy-dependent). The observations are consistent with an overall reduction of the DOS and an increased asymmetry of the generalised conductivity through the Fermi surface. Clearly, we would not expect the broad and relatively featureless bands originating from the Ge framework to display such behaviour. However, recent band structure calculations by Zerec et al. Zerec et al. (2002) have identified the presence of narrow bands with predominant Ba character, which cross the Fermi surface for the undistorted model and are significantly affected by off-site Ba displacement. These band need not contribute greatly to either the overall conductivity or the carrier density, as speculated by Zerec et al. Zerec et al. (2002), as long as one still assumes that enhanced disorder is the main driving force for the resistive anomaly. In summary, the observed changes in transport and magnetic properties can be explained by a reduced relaxation time at low temperatures and a change in the Ba-related bands at the Fermi surface, both effects being consistent with the observed structural behaviour.

### V.3 The spinless bipolaron scenario

Based on the previous considerations, there seems to be no need for additional mechanisms involving strong electron-electron correlation, as proposed by Paschen et al. Paschen et al. (2002). In particular, in the temperature-induced de-trapping scenario, Ba displacement would occur spontaneously, without the need to be associated with a single or a pair of localised electrons. This is not to say that polaron physics is not relevant for this material, since there is clearly strong coupling between the lattice and the conduction electrons. However, low-temperature electronic transport associated with ’jumps’ of Ba atoms between different wells, as proposed by Paschen et al. Paschen et al. (2002), is highly unlikely. This can be shown in a simple manner by estimating the Ba tunneling rate, $`\mathrm{\Gamma }=\mathrm{\Gamma }_0e^{2\lambda }`$ , where $`e^\lambda `$ is the overlap between wavefunctions in the double well, $`\mathrm{\Gamma }_0`$ is a typical phonon frequency and $`\lambda \frac{1}{2}\sqrt{\frac{2mV_0}{\mathrm{}^2}}`$ Anderson et al. (1972). Here, $`V_0`$ is the barrier height and m is the mass of the tunnelling atom. By setting $`V_0=20`$ meV (i.e., of the order of the transition temperature), $`\mathrm{\Gamma }_0=5\times 10^{12}`$ sec-1 and $`m=137m_p`$ we get $`\lambda =14.5`$, $`\mathrm{\Gamma }=0.2`$ sec-1. In other words, the tunnelling rate is macroscopically slow, as expected for heavy atoms such as barium. Therefore, we believe that the low-temperature disorder is essentially static, and cannot be associated with electron hopping. On this point, we make a final consideration: multi-well sites in type-I clathrates were previously associated with glass-like thermal conductivity Chakoumakos et al. (2000); Sales et al. (2001); Nolas et al. (2000); Keppens et al. (2000), through a tunnel-like mechanism. The observation of a crystal-like thermal conductivity in Ba6Ge25, which displays multi-well Ba sites, calls for this proposal to be re-examined. Moreover, one should seriously question whether the tunnelling rates for these heavy-atom systems are sufficiently fast to affect low-temperature heat and electronic transport.

### V.4 Conclusions

We have determined the crystal structure of the Ba6Ge25 clathrate as a function of temperature between 20 and 300K by neutron powder diffraction data. Although the structure was found to be cubic (space group P $`4_1`$ 3 2)at all temperatures, the fully-ordered structural model Carrillo-Cabrera et al. (2000); Fukuoka et al. (2000); Kim et al. (2000) fails to describe the data, particularly at low temperatures. Much better fits are obtained by modelling the nuclear density for two out of the three barium positions (Ba(2) and Ba(3)) with statistically occupied split sites. Ba6Ge25 was found to undergo a significant structural rearrangement around 240K. Although the main effect at the transition is an increase of the distance between split Ba sites on cooling, we have observed significant changes in some of the Ge-Ge bond lengths and angles, indicating strong interactions between the Ba atoms and the Ge framework. The observed structural behaviour can be explained in a simple way by assuming that Ba(2) and Ba(3) are trapped, at low temperatures, within a deep double-well potential, from which they escape when their thermal energy becomes comparable to the barrier height. From our data, the transition appears to be continuous, but the character of the transition is likely to be sample-dependent; other data Paschen et al. (2002) suggest a first-order character, which would require a significant involvement of the Ge framework in the de-trapping process. As far as transport and magnetic properties are concerned, the main consequence of the transition is the enhanced structural disorder on cooling, which is likely to affect significantly all parts of the Fermi surface. This mechanism provides a natural explanation for the drop in electrical conductivity through the transition. The other transport and magnetic anomalies (increase in the absolute value of the negative Seebeck coefficient, decrease in the magnetic susceptibility) can be explained within the framework of the one-electron semi- classical model, by assuming that Ba contributes with narrow bands at the Fermi surface, as confirmed by recent band structure calculations Zerec et al. (2002). Electron-phonon interaction is likely to be strong in Ba6Ge25, which may explain the observation of superconductivity below 1 K Grosche et al. (2001). However, we argue that Ba-site disorder is probably static at low temperatures, suggesting that polaron hopping involving Ba inter-well jumps is unlikely to contribute to the electrical or thermal conductivity.

## VI Acknowledgements

This work was supported in part by US DOE Office of Science grant DE-FG02- 97ER45651. Reproduction of this article, with the customary credit to the source, is permitted. We are grateful to Daniel Khomskii, Alex Shluger and Laurent Chapon for discussing with the authors the results of this work.

## VII Figure captions

Fig. 1 The cubic lattice parameter of Ba6Ge25 as a function of temperature. The error bars mark the standard deviation obtained from refinement. The inset shows the specific resistivity of Ba6Ge25 as a function of temperature.

Fig. 2 Nuclear density at the Ba(2) and Ba(3) sites for Ba6Ge25 at 20K, 200K, 240K and 300K in difference Fourier maps determined from powder diffraction. The maps present the difference between the experimental data and the model with an empty Ba site. The size of all maps is $`5\times 5`$Å2.

Fig. 3 An example of a refined Ba6Ge25 diffraction pattern from the 63 bank. The figure shows the observed intensities (circles), calculated pattern and the difference curve (solid lines). The top and bottom rows of tick marks indicate the positions of graphite and clathrate Bragg reflections respectively. The strongest line of the unidentified impurity is visible at 3.25Å of d-spacing.

Fig. 4 The Ge(1)-Ge(6) and Ge(2)-Ge(3) bond lengths in Ba6Ge25 as a function of temperature. The lines are guide for eye.

Fig. 5 Local environments of Ba(1) and Ba(2) sites in Ba6Ge25 at 20K derived from Rietveld refinement. The Ba(1) resides inside of the distorted dodecahedral cage (Ba atom not shown). The cage has got 3-fold symmetry with the Ge(4), Ge(6) and Ba(1) lying on the rotation axis. The environment of Ba(2) shows both split Ba(2) sites, however only one is occupied at a time. Ba(2) and Ge(6) are located on the 3-fold axis of the unit cell. In the case of Ba(2) site the lines mark the shortest Ba(2)-Ge(3) bonds.

Fig. 6 The Ba(1)-Ge(3), Ba(1)-Ge(4) and Ba(1)-Ge(6) distances in Ba6Ge25 as functions of temperature. The lines are guide for eye.

Fig. 7 The length of the Ba(1) and Ba(2) cages along the 3-fold axis in Ba6Ge25 as a function of temperature. The lines are guide for eye.

Fig. 8 The Ba(2)-Ba(2) and Ba(3)-Ba(3) split site distance in Ba6Ge25 as a function of temperature. The error bars represent the standard deviation obtained from refinement. The lines are guide for eye.

Fig. 9 Local environment of Ba(3) site in Ba6Ge25 at 20K derived from Rietveld refinement. Ba(2) atoms from neighbouring cages are also shown. This cage has 2-fold symmetry, the rotation axis intercepts the Ge(1)-Ge(1) and Ge(4)-Ge(4) bonds in the middle. Only one Ba(3) site is occupied at a time.

Fig. 10 The Ba(2)-Ba(2) split site distance as a function of Ba(3)-Ba(3) split site distance in Ba6Ge25. The solid line is a linear fit as discussed in the text.

Fig. 11 The Ba(2)-Ba(3) shortest distance in Ba6Ge25 as a function of temperature. The line is a guide for eye.

Fig. 12 The quatric double well potential used to demonstrate thermal de-trapping of barium atoms in double-site cages. The potential is bound on both sides by infinite walls, $`V_0`$ denotes the height of potential barrier.


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# ∗∗∗ Temperature Dependence of Optical Spectra for the CDW Gap and Optical Phonons in BaBiO3

\[

## Abstract

We have studied the temperature dependence of the optical spectra for the CDW gap and optical phonons in a single crystal of BaBiO3 and a film deposited by laser ablation. The integrated optical conductivity for optical phonons decreases rapidly with increasing temperature above 150 K, while the single-particle excitation across the CDW gap remains constant.

\] BaBiO3 with a perovskite structure has been known as a mother material for the superconducting Ba1-xKxBiO3 (BKBO), Ba1-xRbxBiO3 (BRBO) of $`T_c`$=30K at x=0.4 and BaPb1-xBixO3 (BPBO) of $`T_c`$=13K at x=0.25. The transition from semiconductor to superconductor occurs with doping. The semiconductivity of BaBiO3 is worth studying in order to elucidate the mechanism of their superconductivity.

BaBiO3 is a semiconductor despite the metallic prediction of the band-structure calculations in the cubic phase.1 In order to explain this energy gap, Charge-Density-Wave (CDW) theory has been introduced. The CDW instability originates from the aversion of Bi to the 4+ valence, which leads to a disproportiontion of Bi3+ (6s2) and Bi5+(6s0) valences on alternate sites. A commensurate CDW with alternately expanded and contracted Bi-O bond lengths on adjacent sites has been found. In the measurement of neutron and X-ray diffraction, Cox and Sleight found that the breathing mode distortion occurs in the real material.2

Experiments to probe the electronic structure of BaBiO3 have been performed by several groups, principally using optical spectroscopy techniques. The energy gap of CDW of 2 eV and four-optical phonons in a far-infrared region were revealed.3,4 Also, an indirect gap corresponding to the activation energy; the 0.24 eV was found in mid-infrared absorption spectra.5

In this paper, we investigate temperature dependences of optical phonons in a far-infrared region and the CDW gap of 2 eV for a single crystals of BaBiO3 prepared by a flux method and for thin films deposited by laser ablation, respectively.

A single crystal of BaBiO3 was prepared by a flux method from a mixture of BaO and Bi2O3 powders. In a furnace, the temperature was increased to 1015C over 8 hours. The temperature was kept at 1015C for 30 minutes, decreased for 15 hours at a rate of 1C/h, and then allowed to decrease to room temperature naturally. Then, single crystals with a sufficiently large area appeared at the surface of the bowl with a golden color. Their crystal structures were found to be monoclinic by means of X-ray diffraction (XRD).

The film were synthesized by laser ablation at the substrate temperature of 600C at the laser-energy density of 2 J/cm2 under an oxygen atmosphere at the pressure of 200 mTorr on the transparent (100)MgO substrate. The thickness of the film was about 280 nm. The laser-ablation system and deposition procedures of the film were explained in a previous paper6.

The reflectances and transmittances of BaBiO3 were observed by using spectrometers with a visible near-infrared and of the Fourier Transformer of Infrared (FTIR). Reflectances were observed in the infrared range of 600 cm-1 (80 meV) from 30 K to 300 K. Transmittances in a visible near-infrared region were observed from 20C to 300C and examined no heat detriment at 50C after heating.

Figure 1 (a)-(g) shows optical conductivities, $`\sigma _{op}`$, of optical phonons observed in the range of 50-600 cm-1 (50-80 meV) at various temperatures. These conductivities were calculated from reflectances by the Kramers-Kronig relation. The conductivities decrease with increasing and decreasing temperature from 150 K. Each peak position of phonons does not significantly vary with temperature. By the relation of the sum rule ($`\sigma _{op}𝑑E`$=$`he^2N_{op}/2m`$), we can define the electronic density, $`N_{op}`$; here, the rest mass of electron is used for a mass, $`m`$. The $`N_{op}`$ is shown in Fig. 2 as a function of temperature, which shows a maximum at 150 K. Since the conventional optical phonons should not exhibit temperature dependence of optical conductivity; this anomalous temperature dependence is attributed to the optical phason proposed by M. J. Rice7. The each phonon decreases $`\sigma _{op}`$ rapidly with temperature above 150 K, as shown in Fig. 3 (a)-(d), here, the phonons are called the phonon 1, 2, 3 and 4 with decreasing order of the wave number. The decrease of the optical conductivity indicates that the electronic density of CDW decreases. The decreased electron density to the electron density of 150 K nearly agrees with the carrier density deduced from the hall effect8. This exhibits that the electronic condensate in the CDW state loose electrons excited to the conduction band, in which the optical spectrum would be broad unobserable. Probably, the decrease of the optical conductivity below 150 K may be due to a structural-phase transition. In the case of 1D-metal such as KCP and K0.3MoO3, peaks in a far-infrared region have been known as the pinned acoustic phason should be searched below 50 cm-1.

Figure 4 (a)-(e) show the transmittances observed near 16000 cm-1 (CDW gap of 2 eV) at various temperatures. The BaBiO3 film deposited by laser ablation was used for the transmittance observation. A thickness of the film was about 280 nm. The transmittances at 17000 cm-1 increase with increasing temperature. The minimum positions (17000 cm-1) of each transmittance do not vary with temperature. A damage at the film occurs above 350C. The transmittance observed at 50C after the heating is nearly the same as that observed at room temperature, as shown in Fig. 4 (e), which indicates that the film is cooled without a damage. The transmittance shows a large conductivities at 20C and 300C were calculated from absorption coefficients calculated from Gauss-Newton numerical analysis, as shown in Fig. 5. The conductivities decrease with increasing temperature at the maximum position. However, the total integrated $`\sigma _{op}`$ remains rather constant all through the temperatures.

In conclusion, we have found the temperature-dependent optical conductivity for phason. This is characteristic of the optical phason in the CDW state of BaBiO3.


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# Impact of Interatomic Electronic Decay Processes on Xe 4d Hole Decay in the Xenon Fluorides

## I Introduction

The Auger effect Auger (1923); Burhop (1980); Thompson et al. (1985); Bambynek et al. (1972, 1974) provides a magnificent means to study atoms, molecules, and surfaces. It is caused by a special type of electronic resonance, i.e., the decay by electron emission of core-ionized atoms, molecules, or solids. Since its discovery it has received much attention, because it is a fundamental process yielding deep insights into complex many-body effects in matter. Moreover, the Auger effect has proven to be useful in many experimental situations Wormeester et al. (1991); Burhop (1980); Thompson et al. (1985); Bambynek et al. (1972, 1974) and can be used as an analytical tool. Therefore, an in-depth understanding of the Auger effect is important both for fundamental and practical reasons.

A particularly interesting situation arises when systems consisting of more than one atom are considered. Can the Auger decay rate of a core hole in an atom be influenced—or maybe even adjusted at will—by modifying the chemical environment of that atom? If yes, what are the underlying mechanisms? Early experiments on gas-phase molecules Shaw, Jr. and Thomas (1972) and ionic solids Friedman et al. (1972) hinted at a simple correlation between the binding energy of a core electron and the Auger width of the associated core hole. For instance, withdrawal of valence electrons by electronegative ligands induces a chemical shift of the core level toward higher binding energies; at the same time, a smaller number of valence electrons is available for Auger decay, if a local, atomic mechanism is assumed. Hence, within the one-center picture of Auger decay Coville and Thomas (1991), an increase in binding energy is accompanied by a decrease in Auger width.

Citrin Citrin (1973), however, analyzed x-ray photoemission measurements in a number of metal oxides and halides, and found convincing evidence for interatomic processes, which can lead to a trend in contradiction to the one-center model. Citrin’s work stimulated theoretical work on interatomic Auger decay in crystalline NaCl Yafet and Watson (1977) and NaF. Green and Jennison (1987) Matthew and Komninos Matthew and Komninos (1975) were the first to present a formal examination of interatomic Auger processes. Using strong approximations, Wormeester et al. (1991) they concluded that these transitions have a small impact on the Auger rate, except in low-energy Auger processes. In fact, recent theoretical and experimental investigations show that in the low-energy case the effect of the chemical bond can be dramatic. Tarantelli et al. (1991); Tarantelli and Cederbaum (1993); Gottfried et al. (1996); Carroll et al. (2002); Thomas et al. (2002)

In this work, we argue that interatomic electronic decay processes can have an even greater impact than previously assumed. We investigate as an example Auger decay of a Xe$`\mathrm{\hspace{0.17em}4}d`$ hole in Xe, XeF2, XeF4, and XeF6. It is demonstrated that the Auger width in the series XeFn, $`n=0,2,4,6`$, would decrease drastically if only intra-atomic decay played a role. By contrast, the experimentally observed linewidths Cutler et al. (1991) display—in clear contradiction to the one-center picture mentioned previously—a monotonic increase from Xe to XeF6. This is illustrated in Fig. 1Thomas (2002) We show that interatomic Auger processes are responsible for the discrepancy. Vibrational broadening, which could cause a similar effect, is very likely to be insignificant. Cutler et al. (1991) Single ionization spectra of the xenon fluorides, which we have calculated recently, Buth (2002); Buth et al. (2003) provided a first theoretical indication of an entirely electronic mechanism.

The xenon fluorides constitute, from our point of view, an ideal example, because of the relatively weak bonding between the central noble-gas atom and the fluorine ligands. This allows us to identify various interatomic decay processes and to distinguish them from the intra-atomic one. In particular, the purely interatomic/intermolecular electronic decay mechanisms that govern the inner-valence physics in weakly bound clusters of atoms or molecules Cederbaum et al. (1997); Santra et al. (2000a); Zobeley et al. (1998, 2001); Santra et al. (2001a, b); Marburger et al. (2003) provide a conceptual framework for our analysis. Therefore, a short summary of these processes is given in Sec. II.

The nature of Auger decay in a molecule can be assessed most clearly by characterizing the available decay channels. To this end, Sec. III introduces a many-body Green’s function method—the algebraic diagrammatic construction scheme Schirmer and Barth (1984); Gottfried et al. (1996)—for calculating double ionization spectra of molecules at a highly correlated level. A two-hole population analysis Tarantelli et al. (1991, 1992) is discussed that serves as an important tool for determining the localization properties of the two holes in an Auger decay channel. Using Wigner-Weisskopf theory, Sakurai (1994); Weisskopf and Wigner (1930) we derive a relationship between final-state population numbers and partial Auger widths. The calculated double ionization spectra are analyzed in Sec. IV, and the relevance of interatomic decay processes for the decay of Xe$`\mathrm{\hspace{0.17em}4}d`$ vacancies is elucidated. Concluding remarks are the subject of Sec. V.

## II Electronic Decay Processes in Weakly Bound Systems

In this section, we review the knowledge obtained in the study of the electronic decay of inner-valence ionized clusters. The decay processes discovered in clusters, and the associated terminology we use in order to emphasize the nature of the underlying mechanisms, allow a succinct classification of the Auger processes in XeFn. We mention that the decay processes discussed in the following for singly ionized systems can be generalized to describe the decay of inner-valence vacancies of multiply ionized clusters. Zobeley et al. (1998); Santra and Cederbaum (2003)

*Intra-atomic electronic decay* (IAED) is usually the most prominent electronic decay process of core-ionized atoms embedded in molecules or clusters. IAED is, of course, the only Auger process that can take place in an isolated atom. In atoms, this mechanism is well understood: Auger (1923); Burhop (1980); Thompson et al. (1985); Bambynek et al. (1972, 1974) The initial core hole is filled by a (valence) electron and the excess energy is transferred via Coulomb interaction to a second (valence) electron, which is emitted subsequently \[Fig. 2(a)\]. In molecules or clusters, intra-atomic decay is not the only decay process, because other processes can occur that involve neighboring atoms or molecules.

If one removes an inner-valence electron from an isolated atom or molecule, the ionized system cannot, in general, decay by electron emission, for it lies energetically below the double ionization threshold. The situation changes if the monomer is part of a cluster.

The initial inner-valence vacancy is filled by a valence electron of the same monomer and the excess energy is transferred to a second valence electron of a neighboring monomer. This electron is emitted subsequently. See Fig. 2(b) for a schematic representation. The decay process is termed *interatomic* or *intermolecular Coulombic decay* (ICD) for clusters of atoms or clusters of molecules, respectively. It was identified theoretically in several weakly bound clusters: (HF)n clusters, Santra et al. (2001a); Cederbaum et al. (1997); Zobeley et al. (1998); Santra et al. (1999) the HF(H2O)2 cluster, Zobeley et al. (1999) (H2O)n clusters, Cederbaum et al. (1997) Nen clusters, Santra et al. (2000a, 2001b); Scheit et al. (2003) and the NeAr dimer. Zobeley et al. (2001) Further we would like to point out studies of electronic decay after inner-valence ionization of CN- Santra et al. (2000b) and of fluorinated carbanions and their acids. Müller et al. (2002)

ICD of inner-valence holes in clusters is ultrafast, typically taking place on a time scale of the order of $`10`$ fs (see Ref. Santra and Cederbaum, 2002 for a review). Experimental evidence for ICD has been found recently in neon clusters. Marburger et al. (2003) In the context of this paper, it is especially important to note that ICD is highly sensitive to cluster size: The ICD width in Nen clusters, for instance, increases strongly with $`n`$, when a central neon atom carries the initial inner-valence vacancy and the surrounding atoms converge with $`n`$ to the shape of the first coordination sphere in solid neon. Santra et al. (2001b) Clearly, a larger number of nearest neighbors translates into a larger number of dicationic decay channels available for ICD.

The ionization spectra of neon and argon are quantitatively very different from one another (Ref. Zobeley et al., 2001, and references therein). Neon has significantly higher lying single (IP) and double ionization potentials (DIP) compared to argon. The inner-valence Ne$`\mathrm{\hspace{0.17em}2}s`$ IP is larger than the Ne-1Ar-1 DIP in the NeAr dimer. Zobeley et al. (2001) Therefore, an initial Ne$`\mathrm{\hspace{0.17em}2}s`$ vacancy can lead to ICD. However, the Ne$`\mathrm{\hspace{0.17em}2}s`$ vacancy in NeAr can decay in another way, too, because the Ne$`\mathrm{\hspace{0.17em}2}s`$ IP is also larger than the NeAr-2 DIP. In this case, a valence electron from argon drops into the Ne$`\mathrm{\hspace{0.17em}2}s`$ hole and the excess energy is transferred to another valence electron of argon. Upon electron emission, the dimer is left in a NeAr-2 state. This process is called *electron-transfer mediated decay* (ETMD). Zobeley et al. (2001) A schematic representation of the ETMD process is shown in Fig. 2(c). In Ref. Zobeley et al., 2001 it is shown that the contribution of ETMD to the total electronic decay width of an initial Ne$`\mathrm{\hspace{0.17em}2}s`$ vacancy in NeAr is appreciably smaller than the contribution of ICD. In light of the vastly increasing ICD width in neon clusters, Santra et al. (2001b) we expect a similar size effect for ETMD, too. In the ETMD described, only two atoms are involved. It is called *two-monomer ETMD* (ETMD2).

A *three-monomer ETMD* (ETMD3) has been suggested to occur for an initial Ne$`\mathrm{\hspace{0.17em}2}s`$ vacancy in NeAr2Zobeley et al. (2001) A schematic representation of this (proposed) process is given in Fig. 2(d). A valence electron of one of the two argon atoms is transferred into the initial Ne$`\mathrm{\hspace{0.17em}2}s`$ hole. Energy is released, and a valence electron is ejected from the second argon atom, leaving the trimer in a NeAr-1Ar-1 state.

We would like to study a new example for the surprising impact of the ideas presented so far. To this end, we examine the decay of Xe$`\mathrm{\hspace{0.17em}4}d`$ vacancies in XeFn and demonstrate how interatomic processes lead to an increase in Auger width. In order to pursue this issue, we need to introduce a few computational techniques and useful relations in the ensuing section.

## III Computational Methods and Basic Relations

### III.1 Algebraic Diagrammatic Construction and Two-Hole Population Analysis

Many-body Green’s functions are ideal tools for investigating excitation spectra of molecular matter at various stages of ionization. Cederbaum and Domcke (1977); Cederbaum (1998) The two-particle Green’s function, specifically, provides direct access to double ionization spectra and associated eigenstates. Algebraic diagrammatic construction (ADC) is an advanced perturbation-theoretical approximation scheme for evaluating many-body propagators. Schirmer (1982); Schirmer et al. (1983); Schirmer and Barth (1984); Schirmer and Angonoa (1989) ADC($`n`$) sums all Feynman diagrams up to $`n`$th order as well as certain classes of diagrams up to infinite order. There is no Dyson equation for the two-particle Green’s function. Brand and Cederbaum (1996, 1998, 2001) The two-particle ADC evaluates the two-particle propagator directly in terms of a Hermitian eigenvalue problem. Schirmer and Barth (1984) The program Tarantelli  we use to calculate double ionization potentials implements the two-particle ADC(2) scheme. Schirmer and Barth (1984)

The two-hole population analysis, utilized in combination with the ADC(2) program, Tarantelli  is a means to reveal the spatial localization of the two holes resulting from double ionization. Tarantelli et al. (1991, 1992) The analysis is carried out in a Mulliken-type Szabo and Ostlund (1982) fashion by determining the atomic two-hole ($`2h`$) contributions to the dicationic eigenstates. To this end, a dicationic eigenstate in the ADC(2) scheme is first expanded in terms of $`2h`$ configurations in molecular orbital basis,

$$|\mathrm{\Psi }_n^{N2}=\underset{ij}{}(\stackrel{}{X}_n)_{ij}|ij+\mathrm{},$$
(1)
where $`\stackrel{}{X}_n`$ is the 2$`h`$ part of the ADC eigenvector of the $`n`$th dicationic state $`|\mathrm{\Psi }_n^{N2}`$. The symbol $`|ij`$ denotes a spin-adapted $`2h`$ configuration with holes in molecular (spin) orbitals $`i`$ and $`j`$, both of which are occupied in the Hartree-Fock ground state of the $`N`$-electron system. Note that $`ij`$ runs only over distinguishable $`2h`$ configurations. Each $`2h`$ configuration in molecular orbital basis, $`|ij`$, can now be expanded Tarantelli et al. (1991, 1992) in terms of 2$`h`$ configurations $`|\mu \nu `$ deriving from the atomic orbital basis

$$|ij=\underset{\mu \nu }{}U_{\mu \nu ,ij}|\mu \nu .$$
(2)
Using this transformation, the total 2$`h`$ weight $`\stackrel{}{X}_n^{}\stackrel{}{X}_n`$ (2$`h`$ pole strength) of the $`n`$th dicationic eigenstate can be written as Tarantelli et al. (1991, 1992)

$$\stackrel{}{X}_n^{}\stackrel{}{X}_n=\stackrel{}{Y}_n^{}𝑶\stackrel{}{Y}_n=\underset{\mu \nu }{}\left[\underset{Q_{\mu \nu ,n}}{\underset{}{Y_{\mu \nu ,n}\underset{\rho \sigma }{}𝑶_{\mu \nu ,\rho \sigma }Y_{\rho \sigma ,n}}}\right],$$
(3)
with eigenvector expansion coefficients $`\stackrel{}{Y}_n:=𝑼\stackrel{}{X}_n`$ in atomic orbital basis. $`𝑶`$ represents the overlap matrix between atomic $`2h`$ configurations, which satisfies $`𝑼^{}𝑶𝑼=\mathrm{𝟙}`$.

On choosing suitable sets of atomic basis functions $`A`$ and $`B`$, one obtains population numbers Tarantelli et al. (1991, 1992) $`Q_{AB,n}=\underset{\genfrac{}{}{0pt}{}{\mu A}{\nu B}}{}Q_{\mu \nu ,n}`$. Frequently, as is done in this work, $`A`$ and $`B`$ represent the atomic basis functions associated with two not necessarily distinct atoms within a molecule. In this sense, $`A`$ and $`B`$ can be identified with individual atoms. This provides a clear picture of the localization properties of the two holes.

### III.2 Relation between Two-Hole Population Numbers and Partial Decay Widths

A useful approximation to the decay width of a resonance is given within the framework of Wigner-Weisskopf theory, Sakurai (1994); Weisskopf and Wigner (1930) which is founded on time-dependent perturbation theory. Applications of Wigner-Weisskopf theory to the electronic decay of inner-valence-ionized clusters can be found in Refs. Santra et al., 2001b and Zobeley et al., 2001. There, single Hartree-Fock determinants were employed to describe both initial and final states. For more complicated systems like XeFn and on the energy scale of core levels, however, the final states in particular require a more sophisticated treatment.

Let the initial state $`|\mathrm{\Psi }_\mathrm{I}^{N1}`$ be a discrete, singly ionized state approximating the core-hole resonance and a final state be a doubly ionized state $`|\mathrm{\Psi }_n^{N2}`$ together with a decay electron of momentum $`\stackrel{}{k}`$. For simplicity we employ the sudden approximation (Ref. Hedin and Lee, 2002, and references therein) and express such a final state by the antisymmetrized product $`\widehat{c}_\stackrel{}{k}^{}|\mathrm{\Psi }_n^{N2}`$, where $`\widehat{c}_\stackrel{}{k}^{}`$ is a fermionic creation operator. Fetter and Walecka (1971) The decay width is then given by

$$\mathrm{\Gamma }=2\pi \underset{n}{}\underset{\stackrel{}{k}}{}|\mathrm{\Psi }_n^{N2}|\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}|^2\delta (E_{n\stackrel{}{k}}E_\mathrm{I}).$$
(4)
This equation contains three types of matrix elements: transition matrix element $`\mathrm{\Psi }_n^{N2}|\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}`$; initial-state energy $`E_\mathrm{I}:=\mathrm{\Psi }_\mathrm{I}|\widehat{H}|\mathrm{\Psi }_\mathrm{I}`$; and final-state energy $`E_{n\stackrel{}{k}}:=\mathrm{\Psi }_n^{N2}|\widehat{c}_\stackrel{}{k}\widehat{H}\widehat{c}_\stackrel{}{k}^{}|\mathrm{\Psi }_n^{N2}`$. The operator $`\widehat{H}`$ is the Hamiltonian in fixed-nuclei approximation. The $`\delta `$ function in Eq. (4) ensures that the contribution to the total decay width of only those accessible final states is summed that conserve energy in the decay.

Using Eq. (1), we obtain

$$\mathrm{\Psi }_n^{N2}|\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}=\underset{ij}{}(\stackrel{}{X}_n^{})_{ij}ij|\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}+\mathrm{}$$
(5)
for the transition matrix elements in Eq. (4). Let us assume that the initial state can be approximated by a single determinant $`|\mathrm{\Psi }_\mathrm{I}^{N1}=\widehat{c}_l|\mathrm{\Phi }_0^N`$, where $`l`$ indicates a core orbital and $`|\mathrm{\Phi }_0^N`$ the $`N`$-electron Hartree-Fock ground state. Let us further exploit the fact that excitations of core orbitals are, to a good approximation, negligible in all expansion terms of the dicationic final state $`|\mathrm{\Psi }_n^{N2}`$. The terms indicated in Eq. (5) with “$`\mathrm{}`$” then vanish exactly due to the Slater-Condon rules. Szabo and Ostlund (1982)

To proceed, we express the dicationic electronic configurations in terms of atomic $`2h`$ vectors $`|\mu \nu `$. The configurations $`|ij`$ appearing in Eq. (5) form an orthonormalized set of functions, and by using the relation

$$|ij=\underset{\mu \nu ,\rho \sigma }{}(𝑶^{\frac{1}{2}})_{\mu \nu ,\rho \sigma }U_{\rho \sigma ,ij}|\mu \nu ,$$
(6)
we introduce an *orthonormalized* set of configurations $`|\mu \nu `$ referring to atomic orbitals. Notice that the atomic configurations in Eq. (2) are not orthonormalized. Inserting Eq. (6) into Eq. (5) leads to

$$\mathrm{\Psi }_n^{N2}|\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}=\underset{\mu \nu }{}(\stackrel{}{Y}_n^{})_{\mu \nu }\mu \nu |\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1},$$
(7)
where $`\stackrel{}{Y}_n^{}:=𝑶^{\frac{1}{2}}𝑼\stackrel{}{X}_n`$. This equation relates the transition matrix element to a superposition of atomic-like quantities.

We now insert the transition matrix element (7) into the basic Eq. (4) for the decay width, integrate over the momentum $`\stackrel{}{k}`$ of the emitted electron, and neglect interference terms (cross terms). The result reads

$$\begin{array}{ccc}\hfill \mathrm{\Gamma }& =& \underset{n}{}\mathrm{\Gamma }_n,\hfill \\ \hfill \mathrm{\Gamma }_n& =& \underset{\mu \nu }{}|T_{\mu \nu }|^2|Y_{\mu \nu ,n}^{}|^2.\hfill \end{array}$$
(8)
The partial width $`\mathrm{\Gamma }_n`$ associated with the final dicationic state $`|\mathrm{\Psi }_n^{N2}`$ is expressed as a sum over atomic $`2h`$ configurations. Each contributing term consists of a state-specific factor $`|Y_{\mu \nu ,n}^{}|^2`$, which we have calculated earlier. The other factor,

$$|T_{\mu \nu }|^2=2\pi \underset{\stackrel{}{k}}{}|\mu \nu |\widehat{c}_\stackrel{}{k}\widehat{H}|\mathrm{\Psi }_\mathrm{I}^{N1}|^2\delta (E_{n\stackrel{}{k}}E_\mathrm{I}),$$
(9)
depends on the dicationic state $`|\mathrm{\Psi }_n^{N2}`$ only via the $`\delta `$ function and is termed transition strength. Since we consider the decay of a core level, implying that the energy of the emitted electron is relatively high, this dependence on $`n`$ is weak and can be neglected to a good approximation.

The state-specific quantities $`|Y_{\mu \nu ,n}^{}|^2`$ are closely related to the occupation numbers discussed in Sec. III.1. In principle, they could be used as an alternative definition of occupation numbers in the spirit of Löwdin’s population analysis. Szabo and Ostlund (1982) In particular, if the atomic basis functions are well localized, each on its atom, we may put $`|Y_{\mu \nu ,n}^{}|^2=Q_{\mu \nu ,n}`$ and obtain

$$\mathrm{\Gamma }_n=\underset{\mu \nu }{}|T_{\mu \nu }|^2Q_{\mu \nu ,n}.$$
(10)
For a given molecule the quantities $`|T_{\mu \nu }|^2`$ are universal, and the only information that is state-specific is contained in the occupation numbers $`Q_{\mu \nu ,n}`$. We are able to compute the occupation numbers of the molecules studied in this work, and hence Eq. (10) is already a useful tool of analysis.

We note, however, that many elements $`|T_{\mu \nu }|^2`$ can be of similar magnitude, e.g., if $`\mu `$ denotes a $`p`$-type atomic orbital on atom $`A`$ and $`\nu `$ a $`p`$-type atomic orbital on atom $`B`$. We therefore group together in Eq. (10) the corresponding contributions: $`\mathrm{\Gamma }_n=|T_{AB}|^2\underset{\genfrac{}{}{0pt}{}{\mu A}{\nu B}}{}Q_{\mu \nu ,n}+\mathrm{}`$. Since the $`|T_{\mu \nu }|^2`$ grouped together are not identical, the average quantity $`|T_{AB}|^2`$ will depend somewhat on the dicationic state index $`n`$. Computing $`\mathrm{\Gamma }=\underset{n}{}\mathrm{\Gamma }_n`$ amounts to averaging over the slightly varying $`|T_{AB}|^2`$ and thus leads to a more stable result.

Highly localized dicationic final-state holes, for example those that result from ICD in weakly bound clusters, lead to similar contributions to the overall decay width of the initially ionized state. By classifying the atomic pairs $`(\mu \nu )`$ by their localization characteristics, we can form sets of atomic orbitals where $`|T_{AB}|^2`$ is only a slightly varying quantity. Let us denote with $`A`$ the atom on which the initial core hole is localized. Then, if $`\mu `$ and $`\nu `$ denote atomic orbitals on $`A`$, $`|T_{\mu \nu }|^2`$ obviously corresponds to IAED (Sec. II). Analogously, if $`\mu `$ belongs to atom $`A`$ and $`\nu `$ to atom $`B`$, we are dealing with ICD, and if neither $`\mu `$ nor $`\nu `$ belong to $`A`$, $`|T_{\mu \nu }|^2`$ describes either ETMD2 or ETMD3, depending on whether $`\mu `$ and $`\nu `$ belong to the same atom $`B`$ or to two atoms $`B`$ and $`C`$. Thus, the *minimal* dissection of $`\mathrm{\Gamma }`$ into its various contributions, in the spirit of the above discussion, reads

$$\mathrm{\Gamma }=\mathrm{\Gamma }_{\mathrm{IAED}}+\mathrm{\Gamma }_{\mathrm{ICD}}+\mathrm{\Gamma }_{\mathrm{ETMD2}}+\mathrm{\Gamma }_{\mathrm{ETMD3}},$$
(11)
where

$$\begin{array}{ccc}\hfill \mathrm{\Gamma }_{\mathrm{IAED}}& =& |T_{\mathrm{IAED}}|^2Q_{\mathrm{IAED}},\hfill \\ \hfill \mathrm{\Gamma }_{\mathrm{ICD}}& =& |T_{\mathrm{ICD}}|^2Q_{\mathrm{ICD}},\hfill \\ \hfill \mathrm{\Gamma }_{\mathrm{ETMD2}}& =& |T_{\mathrm{ETMD2}}|^2Q_{\mathrm{ETMD2}},\hfill \\ \hfill \mathrm{\Gamma }_{\mathrm{ETMD3}}& =& |T_{\mathrm{ETMD3}}|^2Q_{\mathrm{ETMD3}},\hfill \end{array}$$
(12)
and

$$\begin{array}{ccc}\hfill Q_{\mathrm{IAED}}& =& \underset{n}{}\underset{\mu ,\nu A}{}Q_{\mu \nu ,n},\hfill \\ \hfill Q_{\mathrm{ICD}}& =& \underset{n}{}\underset{\genfrac{}{}{0pt}{}{\mu A}{\nu B}}{}Q_{\mu \nu ,n},\hfill \\ \hfill Q_{\mathrm{ETMD2}}& =& \underset{n}{}\underset{\mu ,\nu B}{}Q_{\mu \nu ,n},\hfill \\ \hfill Q_{\mathrm{ETMD3}}& =& \underset{n}{}\underset{\genfrac{}{}{0pt}{}{\mu B}{\nu C}}{}Q_{\mu \nu ,n}.\hfill \end{array}$$
(13)
If necessary, further dissections of $`\mathrm{\Gamma }`$ into more detailed contributions are readily done. For instance, grouping together separately the contributions of $`\mu `$ and $`\nu `$, both being atomic orbitals of $`s`$ type, both of $`p`$ type, or one of $`s`$ and one of $`p`$ type, etc. A distinction between the decay into singlet and triplet final dicationic states is also possible. Finally, we mention that the individual transition strengths, $`|T_{\mathrm{ICD}}|^2`$, etc., may be similar in a series of related molecules.

## IV Results and Discussion

### IV.1 Double Ionization Spectra

The computed double ionization spectra for the xenon atom, the fluorine molecule, and the series XeFn, $`n=2,4,6`$, are shown in Fig. 3. The molecular ground-state geometries used in the calculations are described in Refs. Buth, 2002 and Buth et al., 2003. It has to be stressed, however, that the double ionization spectrum of XeF6, unlike the single ionization spectrum in Refs. Buth, 2002 and Buth et al., 2003, has been calculated assuming a geometry of $`O_h`$ symmetry, instead of $`C_{3v}`$ symmetry, in order to make the calculation feasible with the available computer resources. We also refer the reader to Refs. Buth, 2002 and Buth et al., 2003 for details regarding the Gaussian basis sets employed.

The ADC $`2h`$ pole strength plotted in Fig. 3 characterizes how well the dicationic states are described by $`2h`$ configurations. The deviation of the $`2h`$ pole strength from unity yields the total contribution of three-hole–one-particle configurations to the state in question. Our focus in this work is on the energy regime below the Xe$`\mathrm{\hspace{0.17em}4}d`$ single ionization threshold, which ranges from almost $`68\mathrm{eV}`$ in atomic Xe to a little less than $`76\mathrm{eV}`$ in XeF6Cutler et al. (1991); Buth (2002); Buth et al. (2003) The double ionization spectra below $`80\mathrm{eV}`$ in Fig. 3 comprise ionization out of the outer and inner valence of Xe, F2, and XeFn. Since mean-field and correlation effects, as revealed by the ADC scheme, dominate in the valence region, the spectra have not been corrected for relativistic effects, which are expected to be negligible.

Double ionization from the outer valence of the xenon atom takes place between $`30`$ and $`40\mathrm{eV}`$, and three distinct DIPs are found in Fig. 3. The spectra of the series XeFn, $`n=2,4,6`$, display in this region increasingly dense lying DIPs, which is attributed to a growing number of outer-valence states due to a higher delocalization of the two final-state holes. The double ionization spectrum of F2 in Fig. 3 shows outer-valence ionization of F2 in the range between $`40`$ and $`55\mathrm{eV}`$. With an increasing number of fluorine ligands, the general trend in the spectra, especially at DIPs above $`40\mathrm{eV}`$, is a decrease of the validity of the two-hole description of dicationic states of XeFn. As all fluorine atoms in XeFn are equivalent (the double ionization spectrum of XeF6 is obtained in $`O_h`$ symmetry), a dicationic state with a hole on xenon and a hole on a fluorine atom is in fact a linear combination of configurations involving a hole on xenon and a hole on one of the $`n`$ fluorine atoms in XeFn. The coefficients of the linear combinations are determined by the strength of the interaction among the fluorine ligands, being the weakest in XeF2.

The triple ionization threshold of the xenon atom Mathur and Badrinathan (1987) is $`66.2\mathrm{eV}`$; for the xenon fluorides, the triple ionization threshold is at least that low. Therefore, many of the dicationic states we have calculated can decay to tricationic ones. Owing to the discrete basis set used, the appearance of a decaying state mimics a discretized Lorentzian curve. Zobeley et al. (1998) As can be seen in Fig. 3, such curves may indeed be identified for XeFn above $`50\mathrm{eV}`$. Interestingly, the Xe$`\mathrm{\hspace{0.17em}4}d`$ lines in the single ionization spectra of xenon and its fluorides Cutler et al. (1991); Buth (2002); Buth et al. (2003) are thus above the triple ionization threshold. This indicates that there is some probability for the Xe$`\mathrm{\hspace{0.17em}4}d`$ holes to decay by emitting *two* electrons. According to a measurement by Kämmerling et al.Kämmerling et al. (1992) this probability amounts to about $`20\%`$ in atomic xenon.

When analyzing the DIPs, one has to keep in mind that essentially there are four contributions to a dicationic state that determine its character. The two holes in the dicationic state can be localized on *one* atom, either Xe or F, or on *two* atoms, Xe and F or two different F atoms. The one-site states have a large dicationic population number on either xenon (Xe-2) or a single fluorine (F-2), and the two-site states are of either Xe-1F-1 or F1-1F2-1 character. For each dicationic state appearing in the spectra of the xenon fluorides, the data of the population analysis for equivalent fluorine atoms are summed up to yield the population numbers. In XeF2, for example, the Xe-1F1-1 and Xe-1F2-1 population numbers are added to give a single Xe-1F-1 contribution for each dicationic state in the spectrum of XeF2.

### IV.2 One-site Population Numbers

The one-site population numbers for the xenon fluorides are plotted in Fig. 4. For the graphical representation in Fig. 4 and in Fig. 5, the population numbers have been normalized, i.e., the sum of the contributions of Xe-2, F-2, Xe-1F-1, and F1-1F2-1 character equals unity for each dicationic eigenstate. The spectra are compared to study the effect of the increasing number of fluorine atoms. The first states in the double ionization spectra possess DIPs of $`30\mathrm{eV}`$. The major contribution of the one-site population Xe-2 is at the lower energy part of the spectrum. Obviously, the density of states with a considerable F-2 population increases due to the increasing number of fluorine atoms. The overall distribution of these states does not change much in the different compounds. Certain regions are visible where the states have a high F-2 population. These regions shift slightly to higher DIPs due to the reduced excess charge that the individual fluorine atoms acquire from the central xenon atom in the molecular ground state. Buth (2002); Buth et al. (2003)

Conversely, the importance of Xe-2 contributions to the dicationic states is extremely reduced due to the withdrawal of valence electron density on the xenon atom. In XeF6, the contributions of Xe-2 character have nearly vanished.

### IV.3 Two-site Population Numbers

The two-site population numbers for the xenon fluorides are plotted in Fig. 5. The impact of the increasing number of fluorine atoms is seen here as well. The states with a large F1-1F2-1 population in the spectrum of XeF2 are clearly separated into distinct groups of lines originating from F1$`\mathrm{\hspace{0.17em}2}p^1`$F2$`\mathrm{\hspace{0.17em}2}p^1`$, F1$`\mathrm{\hspace{0.17em}2}p^1`$F2$`\mathrm{\hspace{0.17em}2}s^1`$, and F1$`\mathrm{\hspace{0.17em}2}s^1`$F2$`\mathrm{\hspace{0.17em}2}s^1`$ populations. This can be concluded from a simple energy consideration. The IPs for ionization from molecular orbitals with F$`\mathrm{\hspace{0.17em}2}p`$ character are located at $`20\mathrm{eV}`$, those for ionization from molecular orbitals with F$`\mathrm{\hspace{0.17em}2}s`$ character are located at $`40\mathrm{eV}`$Buth (2002); Buth et al. (2003) In the spectrum of XeF2 in Fig. 5, the groups are approximately at 40, 60, and $`80\mathrm{eV}`$. XeF2 is a linear molecule, the two fluorine atoms being separated by the central xenon atom. Such states with a large F1-1F2-1 population are termed *opposite* F1-1F2-1 states.

The situation changes in XeF4 and XeF6. There are *adjacent* and opposite F1-1F2-1 states, and the clear separation between the groups seen in the spectrum of XeF2 is lost. One reason for this effect is the interaction between adjacent fluorine atoms, which is stronger than the interaction between opposite ones. This leads to a splitting of the fluorine lines, which is also observed in the single ionization spectra. Buth (2002); Buth et al. (2003)

The F1–F2 distance in adjacent F1-1F2-1 states is considerably reduced in comparison to the F1–F2 distance in opposite states, and the hole–hole repulsion energy varies accordingly. Of course, one has to compare states which have a large F1-1F2-1 population that arises from the same types of orbitals. Such F1-1F2-1 states are distributed over a small energy range in the double ionization spectrum. Corresponding lines in XeF2 mark the lower ends of such DIP ranges, due to the maximum distance between the two vacancies. Coulomb repulsion between holes on adjacent fluorine ligands in XeF4 and XeF6 results in shifts toward higher DIPs.

States with a large Xe-1F-1 population do not group like those of F1-1F2-1 character. The density of these Xe-1F-1 states also increases with an increasing number of fluorine atoms, but they are distributed more uniformly over the whole spectral range. In XeF2 and XeF6, these states are dominant with respect to population number, and in XeF4 they are comparable to the F1-1F2-1 states. The DIPs of the Xe-1F-1 states are not subject to a change of the hole–hole repulsion energy (in contrast to those of the F1-1F2-1 states) because the Xe–F distance is the same for all fluorine ligands within a molecule (remember that the double ionization spectrum of XeF6 was calculated assuming octahedral symmetry).

### IV.4 Xe 4d Linewidth

The electronic decay processes presented in Sec. II are characterized in Sec. III.2 according to their final-state population. Using Eqs. (11), (12), and (13), the analysis of the final-state population numbers allows one to determine the relative importance of IAED, ICD, ETMD2, and ETMD3 for the electronic decay of a Xe$`\mathrm{\hspace{0.17em}4}d`$ hole in XeFn. The partial decay width associated with a given decay process can be viewed, according to Eq. (12), as a product of an averaged Coulomb matrix element and a two-hole population factor related to that process.

We calculated the population factors, as defined by Eq. (13), by summing population numbers up to the energy of the Xe$`\mathrm{\hspace{0.17em}4}d`$ lines obtained in Ref. Buth et al., 2003. The results are collected in Table 1. We see that $`Q_{\mathrm{IAED}}`$ is rather low in the xenon fluorides, especially when compared to the population factors $`Q_{\mathrm{ICD}}`$, $`Q_{\mathrm{ETMD2}}`$, and $`Q_{\mathrm{ETMD3}}`$. Hence, as far as population numbers are concerned, IAED is suppressed, and interatomic decay processes dominate the electronic decay of a Xe$`\mathrm{\hspace{0.17em}4}d`$ hole. Also note the sensitive dependence of all population factors on the number of fluorine ligands.

In order to arrive at a complete picture, the transition strengths in Eq. (12) have to be determined. For this purpose, we make a reasonable assumption: The transition strengths $`|T_{\mathrm{IAED}}|^2`$, $`|T_{\mathrm{ICD}}|^2`$, $`|T_{\mathrm{ETMD2}}|^2`$, and $`|T_{\mathrm{ETMD3}}|^2`$ are universal for xenon and its fluorides. This allows us—utilizing Eqs. (11) and (12)—to take the averaged experimental Xe$`\mathrm{\hspace{0.17em}4}d`$ linewidths, displayed in Fig. 1 and reproduced in Table 3, and the population factors in Table 1 to set up a linear system of four equations for the four unknown transition strengths. The matrix of population factors, however, is extremely ill-conditioned, as its $`𝕃^2`$ condition number, Golub and van Loan (1989) for instance, is $`945`$, which is much larger than unity. This means that the solution of the linear system depends strongly on the accuracy of the population factors.

Therefore, we first determine $`|T_{\mathrm{IAED}}|^2`$ by solving Eqs. (11) and (12) for the xenon atom. We then exploit that both $`|T_{\mathrm{ETMD2}}|^2`$ and $`|T_{\mathrm{ETMD3}}|^2`$ are based on electron transfer between Xe and a fluorine ligand. They are thus expected to be of similar magnitude, so we set $`|T_{\mathrm{ETMD2}}|^2=|T_{\mathrm{ETMD3}}|^2`$. The remaining linear system of three equations and two unknowns can be solved in a stable fashion by a least-squares procedure. Golub and van Loan (1989) The calculated transition strengths for Xe and XeFn are displayed in Table 2. The results are in line with expectations: The transition strength associated with intra-atomic decay is greater by an order of magnitude than the interatomic energy-transfer strength of ICD. $`|T_{\mathrm{ETMD2}}|^2`$ and $`|T_{\mathrm{ETMD3}}|^2`$, which require interatomic orbital overlap for electron transfer, are even smaller.

Finally, by combining the population factors from Table 1 and the transition strengths from Table 2, the partial widths $`\mathrm{\Gamma }_{\mathrm{IAED}}`$, $`\mathrm{\Gamma }_{\mathrm{ICD}}`$, $`\mathrm{\Gamma }_{\mathrm{ETMD2}}`$, and $`\mathrm{\Gamma }_{\mathrm{ETMD3}}`$ in XeFn can be computed \[Eq. (12)\]. They are presented in Table 3. The conclusions that can be drawn from this table are truly remarkable. From Xe to XeF6, the contribution from IAED to the total Xe$`\mathrm{\hspace{0.17em}4}d`$ decay width drops monotonically, consistent with the one-center picture mentioned in Sec. I. However, that decrease is more than compensated for by interatomic decay, which is the reason why an overall increase in Xe$`\mathrm{\hspace{0.17em}4}d`$ width is observed in experiment. ICD is the most important interatomic decay mechanism. In XeF4, $`\mathrm{\Gamma }_{\mathrm{ICD}}`$ is already greater than $`\mathrm{\Gamma }_{\mathrm{IAED}}`$, and in XeF6, more than $`50\%`$ of the total Xe$`\mathrm{\hspace{0.17em}4}d`$ width are caused by ICD. Decay via electron transfer is less significant. Nevertheless, while ETMD2 is practically negligible throughout, $`\mathrm{\Gamma }_{\mathrm{ETMD3}}`$ and $`\mathrm{\Gamma }_{\mathrm{IAED}}`$ in XeF6 are in fact comparable, due to the steep rise of the population factor $`Q_{\mathrm{ETMD3}}`$ between XeF2 and XeF6 (Table 1).

## V Conclusion

We have shown that interatomic electronic decay processes are of prime importance for understanding relaxation of a Xe$`\mathrm{\hspace{0.17em}4}d`$ vacancy in the xenon fluorides. The experimentally observed trend of increasing Auger width in the series XeFn, $`n=0,2,4,6`$, is an impressive consequence of the fact that interatomic Coulombic decay and electron-transfer mediated decay not only cancel out the drop in intra-atomic Auger rate: Interatomic decay dominates by far in the larger xenon fluorides. In XeF6, for example, $`76\%`$ of the total Xe$`\mathrm{\hspace{0.17em}4}d`$ linewidth is due to the combined effect of ICD, ETMD2, and ETMD3.

ICD in XeFn takes place on an ultrashort time scale of less than 10 fs. This is of the same order of magnitude as the ICD lifetimes calculated for a $`2s`$ hole in a Ne atom surrounded by at least six neon monomers. Santra et al. (2001b) Our finding that, in XeF6, $`\mathrm{\Gamma }_{\mathrm{ICD}}`$ is only a little more than two times greater than $`\mathrm{\Gamma }_{\mathrm{ETMD3}}`$, affords a new impulse for cluster and condensed-matter research. We anticipate ETMD3 to be a major decay mechanism for an inner-valence hole, for instance, in a neon atom embedded in an argon matrix.

There are obvious consequences of our investigation for molecules bearing a similarity to XeFn. An interesting example is Auger decay of a Si$`\mathrm{\hspace{0.17em}2}p`$ hole in SiF4. It was shown in Refs. Tarantelli and Cederbaum, 1993 and Gottfried et al., 1996 that virtually not a single dicationic (valence) eigenstate in SiF4 is, at a significant level, of Si-2 character. The occurrence of primarily multi-center decay channels is termed *foreign imaging*. It is these channels to which ICD, ETMD2, and ETMD3 provide access. In light of the present study, we may conclude that the calculation by Larkins, Larkins (1994) based on the one-center model, must be expected to appreciably underestimate the Si$`\mathrm{\hspace{0.17em}2}p`$ Auger width in SiF4. A recent measurement by Thomas et al. Thomas et al. (2002) proves this expectation to be justified: The experimental Si$`\mathrm{\hspace{0.17em}2}p`$ Auger width is more than five times greater than the prediction of the one-center model. The authors of Ref. Thomas et al., 2002 also interpret this discrepancy in terms of interatomic electronic processes.

Our approach to molecular Auger decay, as presented in this paper, lays its emphasis on the decay channels. Though not impossible, an actual computation of Auger widths in such complicated many-electron systems as the xenon fluorides still cannot be carried out in a very reliable and accurate manner. We therefore put to use two highly powerful theoretical tools: the ADC scheme for the two-particle propagator and the two-hole population analysis of dicationic eigenstates. These two methods allow us to concentrate on the mechanisms underlying Auger decay by yielding detailed information about the nature of the available decay channels.

The key relations (11), (12), and (13) between two-hole population numbers and partial Auger widths are, strictly speaking, only valid for molecules with pronounced charge localization characteristics. The xenon fluorides satisfy this criterion well. We are convinced, however, that the basic picture is much more general. In order to understand Auger decay in arbitrary molecules, it is usually insufficient to restrict the analysis to local valence electron densities. The physics may be even more complicated, but a qualitative decomposition into interatomic processes ICD, ETMD2, and ETMD3 is most likely still possible.

###### Acknowledgements.

The authors are highly indebted to T. Darrah Thomas for pointing out Ref. Cutler et al., 1991 and supporting it further with valuable private communications (Fig. 1). This work would not have been possible without the ADC programs and support by Francesco Tarantelli. Imke B. Müller, Sven Feuerbacher, Jörg Breidbach, and Thomas Sommerfeld accompanied our work with helpful comments and fruitful discussions. R.S. and L.S.C. gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG).