Interpretation of intermolecular geometric isotope effect in hydrogen bonds: Nuclear orbital plus molecular orbital study

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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.

Original languageEnglish
Pages (from-to)1433-1439
Number of pages7
JournalJournal of Physical Chemistry A
Issue number8
Publication statusPublished - 2011 Mar 3


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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