Table 2.
TT-multiplet simulation parameters for the calculated L-edge and M-edge spectra shown in Figure 3, Figure 4 and Figure S1. In general good fits could be obtained with the given 10 Dq ± 0.15 eV. The satellite features seen in the M2,3 spectra were accounted for by assuming LMCT transitions with Δ = 0 eV and a 60% 4d0 : 40% 4d1L ground state. In order to correctly simulate the M4,5 edge separation using 3d → 5p transitions the 5p L-S coupling was not included for MoO42- and was reduced to 20% of the atomic value for MoS42- as discussed in the text.
| MoO42- | MoS42- | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Edge | Transition | 10Dq | Slater Reduction | Lineshape FWHM (eV) | 10Dq | Slater Reduction | Lineshape (FWHM) (eV) | ||
| Lorentzian | Gaussian | Lorentzian | Gaussian | ||||||
| L2,3 | 2p → 3d | 2.0 | 5% | 2.2 (e, L2) 2.1 (t2, L2) 1.8 (e, L3) 2.5 (t2, L3) |
0.7 | 1.3 | 5% | 2.8 (e, L2) 2.2 (t2, L2) 2.6 (e, L3) 2.4 (t2, L3) |
0.6 |
| M2,3 | 3p → 4d | 2.0 | 30% | 1.8 (e) 2.6 (t2) |
0.04 | 1.3 | 30% | 2.5 (M3) 3.1 (M2) |
0.04 |
| M4,5 | 3d → 5p | – | 80% | 0.40 | 0.04 | – | 30% | 0.40 (M5) 0.46 (M4) |
0.04 |
| M4,5 | 3d → 4f | – | 1% | – | 10% | ||||