Premium
H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H 3 XH … YH 3 (X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation
Author(s) -
Udagawa Taro,
Tachikawa Masanori
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23978
Subject(s) - deuterium , chemistry , intermolecular force , kinetic isotope effect , crystallography , hydrogen bond , hydrogen , isotope , valence (chemistry) , hydrogen atom , molecule , atomic physics , physics , alkyl , organic chemistry , quantum mechanics
Three different H/D isotope effect in nine H 3 XH(D) … YH 3 (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 H 3 CH(D) … YH 3 (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 (CH(D)) bonds and the elongation of intermolecular R (H(D) … Y) and R (C … Y) distances. Second, in the case of H 3 XH(D) … YH 3 (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 H 3 XH(D) … BH 3 (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.