The strongest singlet excitation energies calculated for models 1–4 compared to experimental data.40 The excitation energies and oscillator strengths calculated at the TDDFT and CC2 levels. Molecular orbital contributions and the character of the transitions are also given.
| System | Method | λ calc/nm | f a | Contributionb | Transition type |
|---|---|---|---|---|---|
| [AuCl(CNH)] (1) | SCS-CC2 | 199 | 0.4973 | 18a → 20a (35) | LLCT(pz → π*) |
| 17a → 21a (35) | LLCT(pz → π*) | ||||
| PBE | 265 | 0.2550 | 18a → 20a (45) | LLCT(pz → π*) | |
| 17a → 19a (45) | LLCT(pz → π*) | ||||
| B3LYP | 222 | 0.223 | 17a → 20a (44) | LLCT(pz → π*) | |
| 18a → 19a (44) | LLCT(pz → π*) | ||||
| [AuCl(CNH)]2 (5) | SCS-CC2 | 238 | 0.4243 | 36a → 40a (61) |
|
| 36a → 38a (21) |
|
||||
| PBE | 238 | 0.2551 | 36a → 40a (44) |
|
|
| 36a → 38a (21) |
|
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| B3LYP | 257 | 0.1296 | 36a → 37a (85) |
|
|
| 241 | 0.1341 | 35a → 37a (57) |
|
||
| [AuCl(CNH)]4 (9) | SCS-CC2 | 263 | 1.3934 | 72a → 78a (71) |
|
| 72a → 74a (21) |
|
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| PBE | 321 | 0.4311 | 72a → 73a (96) |
|
|
| B3LYP | 270 | 0.7256 | 72a → 73a (95) |
|
|
| [AuCl(CNCH3)]2 (6) | SCS-CC2 | 217 | 0.3767 | 42a → 46a (53) |
|
| 42a → 44a (20) |
|
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| PBE | 228 | 0.382 | 40a → 46a (34) |
|
|
| 39a → 45a (20) |
|
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| B3LYP | 242 | 0.1563 | 42a → 43a (84) |
|
|
| [AuCl(CNCy)]2 (7) | SCS-CC2 | 238 | 0.3559 | 70a → 74a (53) |
|
| 70a → 73a (14) |
|
||||
| PBE | 234 | 0.5375 | 69a → 74a (34) |
|
|
| 67a → 73a (25) |
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| B3LYP | 245 | 0.1590 | 67a → 71a (92) |
|
|
| 234 | 0.1094 | 66a → 71a (57) |
|
||
| [AuCl(CNCy)]2 | Solid50 | 280 |
a
Oscillator strength.
b
Values are |coeff.|2 × 100.