H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H3XH…YH3 (X = C,Si, or Ge,and Y = B,Al, or Ga) with multicomponent calculation |
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Authors: | Taro Udagawa Masanori Tachikawa |
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Affiliation: | 1. Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Gifu, Japan;2. Quantum Chemistry Division, Graduate School of Science, Yokohama City University, Yokohama, Japan |
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Abstract: | Three different H/D isotope effect in nine H3XH(D)…YH3 (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen‐bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H3CH(D)…YH3 (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C? H(D)) bonds and the elongation of intermolecular R(H(D)…Y) and R(C…Y) distances. Second, in the case of H3XH(D)…YH3 (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge‐inverted hydrogen‐bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)…Y) and R(X…Y) distances. Finally, in the case of H3XH(D)…BH3 (X = Si or Ge) HB systems, these intermolecular R(H(D)…Y) and R(X…Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed. © 2015 Wiley Periodicals, Inc. |
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Keywords: | H/D isotope effect multicomponent calculation charge‐inverted hydrogen bond Ubbelohde effect |
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