Table 1 Composition (%) of the M–E σ bonding NLMOs of [C]=M=E ([C]=C(PH2NSiH3)2; M=Ce, Th, U; E=C(CH3)2, NCH3, O) at their optimised geometriesa
From: Emergence of the structure-directing role of f-orbital overlap-driven covalency
E | M | Functional | Contribution of M to the σ-bonding NLMO | Total d | Total f | ||||
|---|---|---|---|---|---|---|---|---|---|
M | s | p | d | f | |||||
C(CH3)2 | Ce | PBE0 | 31.19 | 1.48 | 0.09 | 63.74 | 34.66 | 19.88 | 10.81 |
PBE | 30.41 | 2.84 | 0.09 | 60.05 | 37.00 | 18.26 | 11.25 | ||
Th | PBE0 | 23.09 | 7.19 | 0.44 | 78.05 | 14.31 | 18.02 | 3.30 | |
PBE | 24.17 | 8.29 | 0.47 | 75.73 | 15.50 | 18.30 | 3.75 | ||
U | PBE0 | 28.89 | 8.32 | 0.24 | 61.19 | 30.25 | 17.68 | 8.74 | |
PBE | 30.56 | 10.59 | 0.21 | 56.83 | 32.36 | 17.37 | 9.89 | ||
NCH3 | Ce | PBE0 | 19.58 | 3.75 | 0.14 | 69.97 | 26.13 | 13.70 | 5.12 |
PBE | 18.61 | 4.65 | 0.17 | 67.37 | 27.80 | 12.54 | 5.17 | ||
Th | PBE0 | 15.36 | 6.57 | 0.95 | 75.09 | 17.35 | 11.53 | 2.66 | |
PBE | 15.86 | 7.13 | 1.07 | 73.30 | 18.48 | 11.63 | 2.93 | ||
U | PBE0 | 19.18 | 7.91 | 0.28 | 60.01 | 31.77 | 11.51 | 6.09 | |
PBE | 19.67 | 11.25 | 0.32 | 59.94 | 28.48 | 11.79 | 5.60 | ||
O | Ce | PBE0 | 26.60 | 3.04 | 0.38 | 32.90 | 63.53 | 8.75 | 16.90 |
PBE | 26.47 | 3.02 | 0.45 | 31.33 | 65.14 | 8.29 | 17.24 | ||
Th | PBE0 | 16.11 | 1.48 | 4.92 | 59.70 | 33.77 | 9.62 | 5.44 | |
PBE | 16.80 | 1.73 | 5.32 | 56.38 | 36.49 | 9.47 | 6.13 | ||
U | PBE0 | 24.20 | 1.73 | 0.59 | 22.84 | 74.79 | 5.53 | 18.10 | |
PBE | 23.94 | 1.42 | 0.58 | 22.44 | 75.52 | 5.37 | 18.08 | ||
