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ab initio determination of bond dissociation energies: The first‐row diatomics co, N 2 , NO, O 2 , and F 2
Author(s) -
Binkley J. S.,
Frisch M. J.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560240837
Subject(s) - diatomic molecule , basis set , chemistry , dissociation (chemistry) , bond dissociation energy , ab initio , molecule , atomic physics , generalized valence bond , valence (chemistry) , computational chemistry , molecular physics , bond length , bond order , physics , density functional theory , organic chemistry
The basis set convergence of the bond dissociation energies of the first‐row diatomic molecules CO, N 2 , NO, O 2 , and F 2 has been studied using fourth‐order Møller–Plesset theory (MP4). Starting with a split‐valence plus polarization basis set, improvements in the basis set are considered which involve expansion of the valence portion to triple‐zeta quality, addition of diffuse s and p functions, expansion to multiple sets of d ‐type polarization functions, and the inclusion of f ‐type functions. For F 2 , which contains a single bond, the addition of diffuse s and p functions has the most important effect on the dissociation energy. The dissociation energies of the remaining molecules, which all involve multiple bonds, are strongly affected by inclusion of multiple sets of d functions and a set of f functions. The largest basis set used provides bond dissociation energies for these molecules that are in close agreement with spectroscopic data.