# Electronic Structure of Cu1-xNixRh2S4 and CuRh2Se4: Band Structure Calculations, X-ray Photoemission and Fluorescence Measurements

## I Introduction

Spinel compounds exhibit an extensive variety of interesting physical properties and have potential technological applications. There are a variety of 3d ion-based oxide spinels, while the S and Se counterparts usually contain 4d or 5d atoms. Several of the compounds are superconductors (LiTi<sub>2</sub>O<sub>4</sub>, CuRh<sub>2</sub>S<sub>4</sub>, CuRh<sub>2</sub>Se<sub>4</sub>, etc.), there are unusual magnetic insulators (e.g. LiMn<sub>2</sub>O<sub>4</sub> and Fe<sub>3</sub>O<sub>4</sub>), and recently, the first d-electron-based heavy fermion metal has been discovered (LiV<sub>2</sub>O<sub>4</sub>). The suprisingly high value of the superconducting critical temperature (11 K) in LiTi<sub>2</sub>O<sub>4</sub> has never been understood. Another spinel compound, CuIr<sub>2</sub>S<sub>4</sub>, is neither magnetic nor superconducting but displays a rather unusual metal-insulator transition that is not yet understood. The ternary sulfo- and selenospinels CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub> have been found to be superconducting at T<sub>c</sub> = 4.70 and 3.48 K, respectively. They have the typical spinel structure \[$`Fd\overline{3}m`$\] where Cu ions occupy the $`A`$ tetrahedral sites and Rh ions occupy the $`B`$ octahedral sites.

This wide range of phenomena in the spinel-structure oxide compounds raises very general questions about the electronic structure of the sulfides and the selenides: are there indications of strong correlations effects, or can their properties be accounted for as Fermi liquids described by conventional band theory? Different models for the valence of Cu in these compounds have been discussed, but according to recent photoemission measurements given for CuV<sub>2</sub>S<sub>4</sub>, CuIr<sub>2</sub>S<sub>4</sub>, CuIr<sub>2</sub>Se<sub>4</sub> and Cu<sub>0.5</sub>Fe<sub>0.5</sub>Cr<sub>2</sub>S<sub>4</sub>, Cu is best characterized as monovalent in spinel compounds. Therefore, one expects that the Rh ion will have a formal mixed valence of +3.5 in CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub>, and indeed both are good metals. However, very little of the typical temperature-dependent behavior of “mixed valence compounds” is seen in these Rh-based spinels.

The electrical and magnetic properties of Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> have been presented by Matsumoto et al. The superconducting transition temperature decreases (4.70 K $``$ 3.7 K $``$ 2.8 K $``$ $`<`$ 2.0 K) as Cu is replaced by Ni (x = 0.00, 0.02, 0.05, and 0.10), but the reason for this behavior is unexplained. Hagino et al. have presented extensive data on CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub> (resistivity, susceptibility, magnetization, specific heat, NMR), but their differences do not yet have any microscopic interpretation. Only for CuRh<sub>2</sub>S<sub>4</sub> have general (full potential, all electron) band structure calculations been reported.

In this paper, we present X-ray spectroscopic studies of the valence band electronic structure of these materials. To provide a clear interpretation of these data, we also report first-principles band structure calculations (Linear-Augmented-Plane-Wave method \[LAPW\]) for CuRh<sub>2</sub>S<sub>4</sub>, CuRh<sub>2</sub>Se<sub>4</sub>, NiRh<sub>2</sub>S<sub>4</sub> and Cu<sub>0.5</sub>Ni<sub>0.5</sub>Rh<sub>2</sub>S<sub>4</sub> that enable us to address the properties of these spinels. Total and partial densities of states (DOS), plasma energies and transport-related quantities are calculated as well as X-ray emission spectra. The total and partial DOS and calculated X-ray emission spectra are found to compare favorably with the measured X-ray photoelectron spectra (XPS) and X-ray emission spectra (XES) (which probe total and partial DOS, respectively). All spectral measurements are performed using the same samples which were used to study the electrical and magnetic properties of Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> in Ref. .

## II Experimental Details

Mixtures of high-purity fine powders of Cu, Ni, Rh, S and Se with nominal stoichiometry were heated in sealed quartz tubes at $`850^{}`$ C for a period of 10 days. Subsequently, the specimens were reground and sintered in pressed parallelepiped form at $`850^{}`$ C for 48 hours. X-ray diffraction data confirms the spinel phase in these powder specimens. The lattice constants of Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> are 9.79, 9.79 and 9.71 Å for x = 0.0, 0.1 and 1.0, respectively, and 10.27 Å for CuRh<sub>2</sub>Se<sub>4</sub>.

The XPS measurements were performed with an ESCA spectrometer from Physical Electronics (PHI 5600 ci, with monochromatized Al-K<sub>α</sub> radiation of a 0.3 eV FWHM). The energy resolution of the analyzer was 1.5$`\%`$ of the pass energy. The estimated energy resolution was less than 0.35 eV for the XPS measurements on the copper and nickel sulfides. The pressure in the vacuum chamber during the measurements was below $`5\times 10^9`$ mbar. Prior to XPS measurements the samples were cleaved in ultra high vacuum. All the investigations have been performed at room temperature on the freshly cleaved surface. The XPS spectra were calibrated using a Au-foil to obtain photoelectrons from the Au-4f<sub>7/2</sub> subshell. The binding energy for Au-4f<sub>7/2</sub> electrons is 84.0 eV.

X-ray fluorescence spectra were measured at Beamline 8.0 of the Advanced Light Source (ALS) at Lawrence Berkeley Laboratory. The undulator beam line is equipped with a spherical grating monochromator, and an experimental resolving power of $`E/\mathrm{\Delta }E=300`$ was used. The fluorescence end station consists of a Rowland circle grating spectrometer. The Ni L<sub>3</sub> and Cu L<sub>3</sub> XES were measured with an experimental resolution of approximately 0.5–0.6 eV and S L<sub>2,3</sub> and Se M<sub>2,3</sub> with resolution of 0.3–0.4 eV. The incident angle of the $`p`$-polarized monochromatic beam on the sample was about $`15^{}`$. The Cu L<sub>3</sub> and Ni L<sub>3</sub> XES were measured just above L<sub>3</sub> threshold but below the L<sub>2</sub> threshold which prevented overlap of the metal L<sub>3</sub> and metal L<sub>2</sub> spectra.

## III Method of Calculation

The band structure calculations were done with the full potential LAPW code WEIN97. The sphere radii were chosen as 2.1 a.u., 2.2 a.u., and 2.0 a.u. for Cu/Ni, Rh, and S/Se, respectively. The plane wave cutoff was K<sub>max</sub> = 3.25 a.u., resulting in slightly more than 1400 basis functions per primitive cell ($``$100 basis functions/atom). The local density approximation (LDA) exchange-correlation potential of Perdew and Wang was used except for the DOS calculations shown in Fig. 7 where the gradient correction to the LDA exchange-correlation potential of Perdew, Burke, and Ernzerhof was used. A mesh of 47 k-points in the irreducible zone (Blöchl’s modified tetrahedron method) was used in achieving self- consistency.

The XES spectra were calculated using Fermi’s golden rule and the matrix elements between the core and valence states (following the formalism of Neckel). The calculated spectra include broadening for the spectrometer and core and valence lifetimes. The DOS calculations used 47 k-points (again, Blöchl’s modified tetrahedron method was used). The experimental lattice constants (listed in the previous section) were used in the calculations and the values used for the internal parameter $`u`$ were taken to be 0.385 for all three stoichiometric compounds (CuRh<sub>2</sub>Se<sub>4</sub>, CuRh<sub>2</sub>S<sub>4</sub>, NiRh<sub>2</sub>S<sub>4</sub>) as well as for Cu<sub>0.5</sub>Ni<sub>0.5</sub>Rh<sub>2</sub>S<sub>4</sub>. Experimental data for the internal parameter was not available, so the values were taken to be 0.385 (rather than the “ideal” position of 3/8) by analogy to the related CuIr<sub>2</sub>S<sub>4</sub> and CuIr<sub>2</sub>Se<sub>4</sub> spinel compounds for which the $`u`$ parameter has been measured.

## IV Discussion of Spectroscopic Data

### A CuRh<sub>2</sub>S<sub>4</sub> and NiRh<sub>2</sub>S<sub>4</sub>

The calculated total and partial DOS of CuRh<sub>2</sub>S<sub>4</sub> and NiRh<sub>2</sub>S<sub>4</sub>, shown in Figs. 1 and 2, reveal many common features. The valence bands extend from E<sub>F</sub> (taken as the zero of energy) to approximately -7 eV and the Fermi level lies near the top of a Rh d-chalcogen p complex of bands that lie below a gap centered 0.5–1.0 eV above the Fermi level. The gap between the valence band and conduction band is found to be about of 0.5–0.7 eV wide. The sulfur states in CuRh<sub>2</sub>S<sub>4</sub> and NiRh<sub>2</sub>S<sub>4</sub> show similar DOS, S 3s atomic-like states in the region -12.7 $``$ -14.7 eV and band-like S 3p states which are mixed with Rh 4d and Cu/Ni 3d-states in a wide energy region. Cu/Ni 3d-states are found to be much narrower than Rh 4d states which are less localized and form two peaks in the DOS near the bottom and the top of the valence band. Our results for CuRh<sub>2</sub>S<sub>4</sub> are similar to those of Ref. 8 except for the distribution of Cu 3d DOS. As seen in Fig. 1, Cu 3d states lie within the region of S 3p states but are weakly hybridized, forming a 1 eV wide peak centered around -2.5 eV. The S d character is quite small and probably reflects tails of the neighboring atoms more than atomic 3d character.

The total DOS at the Fermi level \[N(E<sub>F</sub>)\] increases from NiRh<sub>2</sub>S<sub>4</sub> (8.18 states/eV/cell) to CuRh<sub>2</sub>S<sub>4</sub> (9.89 states/eV/cell) which has the same trend as electronic specific heat coefficients measured in Refs.  and . For the intermediate compound Cu<sub>0.5</sub>Ni<sub>0.5</sub>Rh<sub>2</sub>S<sub>4</sub>, N(E<sub>F</sub>) is 8.43 states/eV/cell, much nearer that of NiRh<sub>2</sub>S<sub>4</sub>. In CuRh<sub>2</sub>S<sub>4</sub> the Cu 3d partial DOS is very small at the Fermi level whereas Rh 4d and S 3p partial DOS are the main contribution to the total. Consequently, the Cooper pairs in the superconducting state of CuRh<sub>2</sub>S<sub>4</sub> are formed mainly by the electrons in the hybridized bands derived from Rh 4d and S 3p states.

In NiRh<sub>2</sub>S<sub>4</sub> the situation is quite different. Ni 3d states are broader and at lower binding energy than the Cu 3d states of CuRh<sub>2</sub>S<sub>4</sub>, and hybridization with S p leads to Ni 3d character over a 3 eV wide region that extends above the Fermi level. The result is that the main contribution to the DOS at the Fermi level is from Ni 3d states, unlike in CuRh<sub>2</sub>S<sub>4</sub> where the Cu 3d contribution at E<sub>F</sub> is very minor.

The experimental Cu L<sub>3</sub> ($`3d4s2p`$ transition), Ni L<sub>3</sub> ($`3d4s2p`$ transition) and S L<sub>2,3</sub> ($`3s3d2p`$ transition) XES probe Cu 3d4s, Ni 3d4s and S 3s3d partial DOS in the valence band and, in the first approximation, can be directly compared with calculated band structures. The comparison of the calculated and measured partial DOS are shown in Figs. 3 and 4, where Cu L<sub>3</sub>, Ni L<sub>3</sub> and S L<sub>2,3</sub> XES are converted to the binding energy scale using our XPS measurements of the corresponding core levels \[E<sub>b.e.</sub>(Cu 2p) = 932.39 eV, E<sub>b.e.</sub>(Ni 2p) = 852.98 eV and E<sub>b.e.</sub>(S 2p) = 161.57 eV\]. We see that the measured Cu L<sub>3</sub>, Ni L<sub>3</sub> and S L<sub>2,3</sub> XES peaks are very close to Cu 3d, Ni 3d and S 3s partial DOS in CuRh<sub>2</sub>S<sub>4</sub> (Fig. 3) and NiRh<sub>2</sub>S<sub>4</sub> (Fig. 4). In each case, the peaks in the calculated DOS lie at somewhat lower binding energy: 1 eV for S 3s and Cu 3p, but only a few tenths of eV for Ni 3d. The difference reflects a self-energy correction that lies beyond our band theoretical methods. In addition, we calculated the emission intensities of Cu/Ni L<sub>3</sub>, Rh N3 ($`4d4p`$ transition) and S L<sub>2,3</sub> XES in both compounds as described in section III. The calculated spectra are presented in the same figures (Figs. 3 and 4) and show close correspondence with experimental spectra as well as with the corresponding partial DOS. From the close agreement, we conclude that the influence of core holes in the measured XES spectra is minor and experimental spectra can be understood directly from the calculated spectra and partial DOS.

### B Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> (x = 0, 0.1, 0.3, 0.5, 1.0)

We measured XPS valence band (VB) spectra for the Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> (x = 0, 0.1, 0.3, 0.5, 1.0) system (see Fig. 5) and found a four peak structure: ($`a`$, $`c`$, $`d`$, $`e`$) for CuRh<sub>2</sub>S<sub>4</sub> and ($`a`$, $`b`$, $`d`$, $`e`$) for NiRh<sub>2</sub>S<sub>4</sub>, each of which is very close to the corresponding calculated total DOS (Figs. 1 and 2). Based on our calculations, we can conclude that the $`a`$ peak at 1 eV binding energy is formed by Rh 4d-S 3p states for CuRh<sub>2</sub>S<sub>4</sub> and Ni 3d-Rh 4d–S 3p states for NiRh<sub>2</sub>S<sub>4</sub>. The next peak ($`b`$ for NiRh<sub>2</sub>S<sub>4</sub> at 2 eV binding energy and $`c`$ for CuRh<sub>2</sub>S<sub>4</sub> at 3 eV binding energy) can be attributed mainly to Ni (respectively Cu) 3d states. The $`d`$ peak (5.5 eV) relates to Rh 4d-S 3p states and the $`e`$ peak is associated with atomic-like S 3s states. In the solid solution Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> the positions of the peaks do not change as the concentration varies, but only the ratio of intensities of $`b`$ (Ni 3d) and $`c`$ (Cu 3d) peaks vary according to the Cu/Ni concentration.

This behavior suggests that the electronic structure of the solid solution Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> can be deduced by analyzing the endpoints (x = 0.0 and 1.0), CuRh<sub>2</sub>S<sub>4</sub> and NiRh<sub>2</sub>S<sub>4</sub>. This conclusion results not from a rigid band picture (which does not hold) but from the opposite “split-band” behavior in which both Cu and Ni retain their own DOS peaks which then vary in strength roughly as the concentration. In Fig. 6 we have compared XPS VB measurements with Cu L<sub>3</sub>, Ni L<sub>3</sub> and S L<sub>2,3</sub> XES spectra for Cu<sub>0.5</sub>Ni<sub>0.5</sub>Rh<sub>2</sub>S<sub>4</sub>. We see that positions of the peaks in the Ni L<sub>3</sub>, Cu L<sub>3</sub> and S L<sub>2,3</sub> XES spectra correspond exactly to peaks $`b`$, $`c`$ and $`e`$ of the XPS VB measurements, which is consistent with our interpretation of the XPS data as indicating a solid solution of Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> if the split-band behavior holds.

In Fig. 7 we have compared the calculated total DOS of CuRh<sub>2</sub>S<sub>4</sub>, NiRh<sub>2</sub>S<sub>4</sub>, and Cu<sub>0.5</sub>Ni<sub>0.5</sub>Rh<sub>2</sub>S<sub>4</sub>. With respect to the top of the highest occupied bands, the Fermi energy is highest in the bands of CuRh<sub>2</sub>S<sub>4</sub> to accommodate the two additional electrons from the Cu atoms. The behavior of the DOS for the three systems shown are quite different, particularly for Cu and Ni ions, in an energy range between the Fermi levels for NiRh<sub>2</sub>S<sub>4</sub> and for CuRh<sub>2</sub>S<sub>4</sub>, invalidating a rigid-band interpretation of the differences and similarities in these compounds. This is not surprising given the different character of the Ni- and Cu-derived states in this energy region. As mentioned above, whereas states at the Fermi level in NiRh<sub>2</sub>S<sub>4</sub> have a strong Ni 3d character, Cu 3d states lie entirely below the Fermi level in CuRh<sub>2</sub>S<sub>4</sub>. The character of states at the Fermi level in CuRh<sub>2</sub>S<sub>4</sub> are primarily Rh d-like states hybridized with S 3p states.

According to Ref. , the superconducting transition temperature of Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> decreases with increasing Ni concentration from 4.7 K (x = 0.0) to 3.7 K (x = 0.02) and then to 2.8 K (x = 0.05). While we attribute this to a general decrease in DOS at the Fermi level as the Ni concentration is increased (see Sec. V), this trend does not require a simple rigid-band interpretation. In the alloy, the DOS within a few tenths of an eV of E<sub>F</sub> probably cannot be described by either the rigid band or split-band models.

### C CuRh<sub>2</sub>Se<sub>4</sub>

Figure 8 shows the calculated total and partial DOS for CuRh<sub>2</sub>Se<sub>4</sub>. While it is similar to that of CuRh<sub>2</sub>S<sub>4</sub> (Fig. 1), we can point out two differences: ($`i`$) the Se 4p DOS is redistributed somewhat compared to S 3p and has a higher contribution in the vicinity of the Fermi level, and ($`ii`$) the Se d-like character is even less than that of the d-like character in CuRh<sub>2</sub>S<sub>4</sub>. The total DOS at the Fermi level is 12.05 states/eV-cell which is higher than in CuRh<sub>2</sub>S<sub>4</sub>, in qualitative agreement with measurements of electronic specific-heat measurements.

In Fig. 9 the experimental Cu L<sub>3</sub> and Se M<sub>2,3</sub> ($`4s3p`$ transition) XES measurements are compared to the Cu 3d and Se 4s partial DOS and calculated spectra. The agreement of the peak positions between experiment and theory is quite close. Again we note that calculated XES spectra exactly follow the partial DOS, as in the case of CuRh<sub>2</sub>S<sub>4</sub> and NiRh<sub>2</sub>S<sub>4</sub> (Figs. 3 and 4). The XPS valence band data is compared with the Cu L<sub>3</sub> and Se M<sub>2,3</sub> XES spectra of Fig. 10. The location of Cu 3d-Se 4s-derived bands is reproduced well (comparable to that in the sulfide) by the calculations. There are some differences in ratio of the XPS peaks for CuRh<sub>2</sub>Se<sub>4</sub> and CuRh<sub>2</sub>S<sub>4</sub>: the relative intensity of Cu 3d peak located of around 2.5 eV is less in CuRh<sub>2</sub>Se<sub>4</sub> than in CuRh<sub>2</sub>S<sub>4</sub>. This may be due to the 2.5 times larger photo-ionization cross-section of Se 4p states as compared to that of S 3p states.

## V Other Data

In a metal the Drude plasma energy tensor $`\mathrm{}\mathrm{\Omega }_{p,ij}`$ contains a good deal of information about low temperature transport and low frequency optical properties. $`\mathrm{\Omega }_{p,ij}`$ is given by

$`\mathrm{\Omega }_{p,ij}^2`$ $`=`$ $`4\pi e^2{\displaystyle \frac{1}{V}}{\displaystyle \underset{k}{}}v_{k,i}v_{k,j}\delta (\epsilon _k\epsilon _F)`$ (1)   
$`=`$ $`4\pi e^2v_iv_jN(\epsilon _F)`$ (2)   
where $`v_{k,i}`$ is the i-th cartesian coordinate of the electron velocity, $`V`$ is the normalization volume and $`\mathrm{}`$ indicates a Fermi surface average. The optical conductivity (specializing now to cubic metals) contains a $`\delta `$-function contribution at zero frequency proportional to $`\mathrm{\Omega }_p^2`$ (which is broadened by scattering processes), and the static conductivity in Bloch-Boltzmann theory becomes

$$\rho (T)=\rho _0+\frac{4\pi }{\mathrm{\Omega }_p^2\tau }$$
(3)   
($`\rho _0`$ is the residual resistivity at T = 0) as long as the mean free path $`l=v_F\tau `$ is large enough that scattering processes are independent. When phonon scattering dominates, which is usually the case above 25$`\%`$ of the Debye temperature, the relaxation time $`\tau `$ becomes approximately

$$\frac{\mathrm{}}{\tau _{ep}}=2\pi \lambda _{tr}k_BT$$
(4)   
where $`\lambda _{tr}`$ is a “transport” electron-phonon (EP) coupling strength that is usually close to the EP coupling constant $`\lambda `$ that governs superconducting properties. Then in the high T regime we obtain the estimate

$$\lambda \lambda _{tr}\frac{\mathrm{}\mathrm{\Omega }_p^2}{8\pi ^2k_B}\frac{d\rho }{dT}$$
(5)   
.

Hagino et al. have presented resistivity data on sintered samples of CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub>. Although both are clearly metallic (d$`\rho `$/dT $`>`$ 0), the magnitudes of $`\rho `$ differ by a factor of 20 over most of the range 50 K $``$ T $``$ 300 K. CuRh<sub>2</sub>Se<sub>4</sub> has $`\rho _0=2\mu \mathrm{\Omega }cm`$, indicating excellent metallic behavior in spite of the intergrain scattering that is present in the sintered samples. The CuRh<sub>2</sub>S<sub>4</sub> sample had $`\rho _0=500\mu \mathrm{\Omega }cm`$ (perhaps from intergrain scattering connected to differences in surface chemistry of the sulfide and the selenide) which makes Eq. (3) inapplicable. Moreover, both materials (especially CuRh<sub>2</sub>S<sub>4</sub>) show saturation behavior which makes the Bloch-Boltzmann analysis less definitive. However, we can apply this formalism to CuRh<sub>2</sub>Se<sub>4</sub> to obtain an estimate, using $`d\rho /dT2\mu \mathrm{\Omega }cm/K`$ to obtain $`\lambda _{tr}=1.8`$. This value is almost a factor of three larger than $`\lambda =0.64`$ found by Hagino et al. to be sufficient to account for T<sub>c</sub> = 3.5 K. We expect that the magnitude of $`\rho `$ measured on the sintered sample of CuRh<sub>2</sub>Se<sub>4</sub>, although small, is still not representative of the bulk.

From their measurements, Hagino et al. inferred almost indistinguishable values of the linear specific heat coefficient $`\gamma `$, the density of states N(E<sub>F</sub>), and electron-phonon coupling strengths $`\lambda `$ for CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub>. Our calculations lead to a 20$`\%`$ higher value of N(E<sub>F</sub>) in the selenide which is at odds with their values. The 1.2 K lower value of T<sub>c</sub> in the selenide is not very definitive, since this difference could be related to softer phonon frequencies. The nearly factor of two increase in the susceptibility in the selenide (and not in the sulfide) below 300 K remains unexplained. Data on single crystal samples may be necessary to resolve these discrepancies.

## VI Conclusions

The main results of the present study of the electronic structure in Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> and CuR<sub>2</sub>Se<sub>4</sub> can be summarized as follows. The electronic states near E<sub>F</sub> consist mainly Rh 4d and S(Se) 3p(4p) orbitals for CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub> and primarily Ni 3d with some Rh 4d and S 3p orbitals in NiRh<sub>2</sub>S<sub>4</sub>. Thus, we find that character of states at the Fermi level changes in a non-rigid-band way in Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub>, and while there is a general trend of a decreasing DOS at the Fermi level as a function of Ni concentration, we have found that the superconducting trends in Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> cannot be explained quantitatively by the calculated DOS of the Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> system. Moreover, such an interpretation would be at odds with the partial DOS which shows the different character of states near E<sub>F</sub>. The measured X-ray data suggests interpreting Cu<sub>1-x</sub>Ni<sub>x</sub>Rh<sub>2</sub>S<sub>4</sub> as a solid state solution more in line with a “split-band” interpretation.

Calculated X-ray emission spectra are found to be in an excellent agreement with experimental data, with peak positions differing by only 0.3–1.0 eV. This agreement implies that core hole effects are negligible. In addition to total DOS, plasma energies have been calculated and used to offer additional theoretical input to interpret the differences between CuRh<sub>2</sub>S<sub>4</sub> and CuRh<sub>2</sub>Se<sub>4</sub>. Unfortunately, transport data appear to be too strongly affected by intergrain scattering to allow a quantitative analysis.

To summarize, the very good agreement between the measured and calculated electronic spectra indicate a lack of any strong correlation effects. The decrease in superconducting T<sub>c</sub> with Ni concentration is likely due to a decrease in N(E<sub>F</sub>). Beyond these general conclusions, however, several questions remain. The linear specific heat coefficients are not accounted for quantitatively; neither are the intermediate temperature resistivities, but these must be measured on single crystals to obtain a good experimental picture. Finally, the temperature dependence of the susceptibility of CuRh<sub>2</sub>Se<sub>4</sub> remains unexplained.

## VII Acknowledgments

This work was supported by the Russian Science Foundation for Fundamental Research (Projects 96-15-96598 and 98-02-04129), a NATO Linkage Grant (HTECH.LG 971222), INTAS-RFBR (95-0565), NSF Grants (DMR-9017997, DMR-9420425, and DMR-9802076), and the DOE EPSCOR and Louisiana Education Quality Special Fund (DOE-LEQSF (1993-95-03)). Work at the Advanced Light Source at Lawrence Berkeley National Laboratory was supported by the U.S. Department of Energy under contract (DE-AC03-76SF00098).