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A large structural polarization by intermolecular forces: Ab initio theoretical investigation of the H 3 N···H 2 CN and H 3 N···B(CN) 3 interactions
Author(s) -
Jagielska Anna,
Moszynski Robert,
Piela Lucjan
Publication year - 1999
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/(sici)1097-461x(1999)75:3<177::aid-qua7>3.0.co;2-g
Subject(s) - chemistry , quadrupole , coupled cluster , ab initio , molecule , dipole , intermolecular force , computational chemistry , perturbation theory (quantum mechanics) , electronic correlation , anharmonicity , basis set , atomic physics , molecular physics , crystallography , density functional theory , quantum mechanics , physics , organic chemistry
The structure, binding energies, harmonic vibrational frequencies, and nuclear quadrupole coupling constants of the cyanodihydroborate and boron tricyanide (known compounds, but no structural experimental data available) complexes with ammonia were calculated using the Møller–Plesset perturbation theory through the fourth order and by the coupled‐cluster method including single, double, and approximate triple excitations. The origins of the bonding in these complexes were investigated by symmetry‐adapted perturbation theory. The computed complex dissociation energies corrected for the basis‐set superposition error are large: 27 and 36 kcal/mol, respectively. A peculiar change of the character of the HOMO orbital is taking place when the molecules approach each other. In both complexes, a large (umbrellalike) structural change of the boron moiety occurs due to the interaction with the virtually unchanged ammonia molecule and the accompanying large change of the dipole moment is taking place. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 177–185, 1999