The vibrational frequencies, the dissociation energy, and the electron affinity of nickel carbonyl
- 1 April 1988
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 88 (7) , 4324-4333
- https://doi.org/10.1063/1.453792
Abstract
CPF, MCPF, and multireference CCI calculations have been done on nickel carbonyl and its positive and negative ions. For obtaining an accurate value of the dissociation energy De of Ni–CO it is important to correlate all the CO valence electrons. The difference in De with and without CO correlation is 17 kcal/mol which is about half of the total De. The best CCI calculation gave a dissociation energy of 33 kcal/mol in good agreement with experiments. The CPF and MCPF dissociation energies were 30 kcal/mol. The largest CCI calculation also gave a frequency shift between CO and NiCO in excellent agreement with experiments, 143 cm−1 compared to 142 cm−1. The effect of coupling the Ni–C and C–O motions is 20 cm−1 on the shift. The calculations on NiCO− show that the added electron enters into the σ symmetry and leads to an almost unchanged Ni–C bond length and a slight reduction of the dissociation energy. When NiCO is ionized on the other hand the removed electron in the σ symmetry causes a large increase of 0.8 a0 in the Ni–C bond length but does not change the dissociation energy.Keywords
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