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Published on: July 19, 2019
Interpretation of intermolecular geometric isotope effect in hydrogen bonds: nuclear orbital plus molecular orbital
Yasuhiro Ikabata1, Yutaka Imamura, Hiromi Nakai
1Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University , Tokyo 169-8555, Japan.
Abstract:
The intermolecular geometric isotope effect (GIE) in hydrogen bond A-X···B (X = H and D) is investigated theoretically using the nuclear orbital plus molecular orbital (NOMO) theory. To interpret the GIE in terms of physically meaningful energy components such as electrostatic and exchange-repulsion interactions, the reduced variational space self-consistent-field method is extended to the NOMO scheme. The intermolecular GIE is analyzed as a two-stage process: the intramolecular bond shrinkage and the intermolecular bond elongation. According to the isotopic shifts of energy components described by the NOMO/MP2 method, the intermolecular GIE is approximately interpreted as a process reducing the exchange-repulsion interaction after the decrease of electrostatic interaction.
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