Table 3. XAS Main Lines (in eV) As Well As Differences between L2,3- and M4,5-Edges Corresponding to SO Splitting, As Obtained from Experiments and 4c-DR-TDDFT (VDZ/aVDZ) Calculations Using the PBE0-XHF Functional, where X Is the Determined Optimal Admixture of HFX.
| PBE0-XHF |
|||||
|---|---|---|---|---|---|
| exp.a | X | energy | error | ||
| VOCl3 | L3 | 516.9 | 50 | 515.2 | –1.7 |
| L2 | 523.8 | 50 | 522.0 | –1.8 | |
| L2–L3 | 6.9 | 6.8 | –0.1 | ||
| CrO2Cl2 | L3 | 579.9 | 50 | 580.0 | 0.1 |
| L2 | 588.5 | 50 | 588.2 | –0.3 | |
| L2–L3 | 8.6 | 8.2 | –0.4 | ||
| MoS42– | L3 | 2521.7 | 60 | 2523.1 | 1.4 |
| L2 | 2626.0b | 60 | 2627.6 | 1.6 | |
| L2–L3 | 104.3 | 104.5 | 0.2 | ||
| M5 | 228.7 | 40 | 228.9 | 0.2 | |
| M4 | 231.7 | 40 | 232.2 | 0.5 | |
| M4–M5 | 3.0 | 3.3 | 0.3 | ||
| PdCl62– | L3 | 3177.8 | 60 | 3173.4 | –4.4 |
| L2 | 3334.7 | 60 | 3332.9 | –1.8 | |
| L2–L3 | 156.9 | 159.5 | 2.6 | ||
| WCl6 | L3 | 10212.2 | 60 | 10207.3 | –4.9 |
| L2 | 11547.0 | 60 | 11561.7 | 14.7 | |
| L2–L3 | 1334.8 | 1354.4 | 19.6 | ||
| ReO4– | L3 | 10542.0 | 60 | 10541.0 | –1.0 |
| L2 | – | 60c | 11982.1 | – | |
| L2–L3 | – | 1441.1 | – | ||
| UO2(NO3)2 | M5 | – | 60c | 3549.9 | – |
| M4 | 3727.0 | 60 | 3728.0 | 1.0 | |
| M4–M5 | – | 178.1 | – | ||
a
Experimental references: VOCl3, ref (61); CrO2Cl2, ref (61); MoS42–, ref (120); PdCl62–, ref (112); WCl6, ref (121); ReO4–, ref (111); UO2(NO3)2, ref (122).
b
Value taken from Figure 3 in ref (120), rather than Table 1 ibid. due to a misprint.
c
Since an experimental reference was not available, we selected 60% HFX as the most likely optimal value on the basis of other spectra in the calibration.