Table 2. Calculated NBO Charge Distribution on TM[Mo3S13]2––2H and V[Mo3S13]2––H2. Mo-1, Mo-2, and Mo-3 Represent Three Mo Atoms, while S-a and S-b Label Two S Atoms That Bind to the Corresponding H Atoms, H-a and H-ba.
| cluster | q(Mo-1) | q(Mo-2) | q(Mo-3) | q(S-a) | q(S-b) | q(TM) | q(H-a) | q(H-b) |
|---|---|---|---|---|---|---|---|---|
| Sc[Mo3S13]2––2H | –0.92 | –1.33 | –1.07 | –0.53 | –0.21 | 0.35 | 0.14 | 0.12 |
| Sc[Mo3S13]2– | –1.02 | –1.30 | –1.02 | –0.29 | –0.05 | 0.35 | ||
| Ti[Mo3S13]2––2H | –1.02 | –1.29 | –0.90 | –0.28 | –0.18 | –0.59 | 0.13 | 0.14 |
| Ti[Mo3S13]2– | –0.89 | –1.26 | –0.94 | –0.06 | –0.09 | –0.65 | ||
| V[Mo3S13]2––H2 | –1.04 | –1.35 | –1.09 | –0.22 | –0.26 | 0.04 | –0.05 | |
| V[Mo3S13]2– | –1.25 | –1.29 | –1.21 | 0.050 | 0.41 | |||
| Cr[Mo3S13]2––2H | –1.18 | –1.29 | –1.23 | –0.25 | –0.35 | 0.50 | 0.10 | 0.15 |
| Cr[Mo3S13]2– | –1.28 | –1.30 | –1.22 | –0.02 | –0.22 | 0.51 | ||
| Mn[Mo3S13]2––2H | –1.07 | –1.31 | –0.96 | –0.65 | –0.02 | 0.67 | 0.12 | 0.16 |
| Mn[Mo3S13]2– | –1.29 | –1.30 | –1.21 | –0.05 | –0.11 | 0.70 | ||
| Fe[Mo3S13]2––2H | –1.12 | –1.31 | –1.13 | –0.21 | –0.61 | 0.53 | 0.11 | 0.13 |
| Fe[Mo3S13]2– | –1.12 | –1.30 | –1.23 | –0.09 | –0.21 | 0.39 | ||
| Co[Mo3S13]2––2H | –1.11 | –1.32 | –0.96 | –0.03 | –0.60 | 0.39 | 0.16 | 0.11 |
| Co[Mo3S13]2– | –1.29 | –1.30 | –1.21 | –0.11 | –0.02 | 0.53 | ||
| Ni[Mo3S13]2––2H | –0.92 | –1.29 | –1.26 | –0.14 | –0.54 | 0.20 | 0.12 | 0.12 |
| Ni[Mo3S13]2– | –1.04 | –1.29 | –1.26 | 0.05 | –0.31 | 0.09 |
a
In the case of molecular adsorption V[Mo3S13]2––H2, both H-a and H-b bind to S-a atom. The corresponding qNBO values without hydrogen adsorption are provided for comparison.