Table 1. Experimental Energetic Data and Deviations for DFT and CCSD(T) Methodsa.
| Energetics
Data (kcal/mol) |
||||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| molecule | propertyb | exp (kcal/mol) | ref | derived expc | B3LYPd | B97-1d | BH&HLYPd | CCSD(T)d,e | CCSD(T)-DKe,f | T1h |
| [Cu(CO)1]+ | sBDE | 35.6 | (90) | 37.1 | +0.6 | +0.0 | –7.2 | –4.4 | –0.5 | 0.0229 |
| [Cu(CO)2]+ | sBDE | 41.1 | (90) | 42.9 | –5.1 | –5.6 | –11.3 | –6.6 | –3.2 | 0.0232 |
| [Cu(CO)3]+ | sBDE | 17.9 | (90) | 19.0 | –1.3 | –0.2 | –4.0 | +0.4 | +1.1 | 0.0237 |
| [Cu(CO)4]+ | sBDE | 12.7 | (90) | 14.0 | –0.7 | +0.6 | –2.9 | +2.6 | +3.2 | 0.0245 |
| [Cu(NH3)1]+ | sBDE | 56.6 | (91) | 59.5 | +0.1 | –0.9 | –5.5 | –4.0 | –0.2 | 0.0226 |
| [Cu(NH3)2]+ | sBDE | 59.3 | (91) | 62.5 | –7.0 | –7.4 | –11.1 | –6.9 | –3.2 | 0.0211 |
| [Cu(NH3)3]+ | sBDE | 11.0 | (91) | 12.4 | +0.7 | +2.0 | +2.7 | +3.9 | +2.2 | 0.0187 |
| [Cu(NH3)4]+ | sBDE | 10.8 | (91) | 12.7 | –2.9 | –1.9 | –1.5 | +0.4 | –0.4 | 0.0169 |
| [Cu(H2O)1]+ | sBDE | 38.4 | (92) | 40.0 | +1.3 | +0.1 | –1.3 | –1.5 | +0.5 | 0.0196 |
| [Cu(H2O)2]+ | sBDE | 40.7 | (92) | 42.7 | –1.4 | –2.6 | –4.6 | –2.8 | +0.2 | 0.0216 |
| [Cu(H2O)3]+ | sBDE | 13.7 | (92) | 15.8 | –2.3 | –1.5 | –0.4 | –0.4 | +1.4 | 0.0191 |
| [Cu(H2O)4]+ | sBDE | 12.8 | (92) | 14.9 | –4.3 | –3.3 | –2.6 | –1.7 | –2.8 | 0.0159 |
| Cu2 | ΔHf0/Eat | 115.3 | (76) | 45.8 | –3.6 | +3.0 | –10.9 | –3.3 | –0.8 | 0.0287 |
| CuH | ΔHf0/Eat | 65.9 | (75) | 68.7 | –5.8 | –5.6 | –11.3 | –6.9 | –4.4 | 0.0392 |
| CuOHg | ΔHf0/Eat | 28.0 | (76) | 169.7 | +7.1 | +10.3 | –7.8 | +7.9 | +8.5 | 0.0390 |
| CuOg | ΔHf0/Eat | 73.2 | (76) | 67.0 | –2.9 | +0.9 | –15.8 | –5.9 | +8.3 | 0.0787 |
| CuSg | ΔHf0/Eat | 75.1 | (76) | 71.5 | –9.2 | –2.7 | –15.2 | –10.3 | –13.2 | 0.0680 |
| Cu | first IP | 178.2 | (93) | 178.2 | +7.1 | –3.0 | –5.4 | –6.6 | –1.5 | 0.0251 |
| Cu | second IP | 468.0 | (93) | 468.0 | +10.4 | +4.5 | –12.3 | –0.1 | –4.0 | |
| MADi | 2.3 | 2.2 | 4.6 | 3.0 | 1.6 | |||||
| MAXi | 7.0 | 7.4 | 11.3 | 6.9 | 3.2 | |||||
Deviations are shown with respect to the derived experimental values.
The term “sBDE” denotes sequential bond dissociation energy at 0 K; the nondissociated molecule is listed in the first column. ΔHf0 represents the heat of formation at 298.15 K, Eat is the atomization energy at 0 K, and IP is the ionization potential. If two properties are specified, the one before the slash refers to the actual experiment, the one after refers to the derived experimental value.
The derived experimental values exclude zero-point energy and thermal corrections as calculated from B3LYP/6-31+G(d,p) vibrational frequencies and the classical approximation (see, e.g., ref (94)) for translations ((3/2)RT) and rotation (RT for linear molecules, (3/2)RT otherwise). For the conversions from heats of formation to atomization energy, the PV term is approximated as RT; the enthalpies of formation for gaseous atoms at 0 K and the heat capacity corrections (H298 – H0) are taken from refs (95) and (75).
aug-cc-pVTZ.
Calculated at B3LYP/aug-cc-pVTZ geometries.
aug-cc-pVTZ-DK.
Experimental uncertainty larger than 4 kcal/mol.
T1 diagnostic calculated at the CCSD(T)/aug-cc-pVTZ level with Molpro.
The error analysis (mean absolute deviation (MAD) and maximal absolute deviation (MAX)) applies only to the Cu(I) compounds.