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
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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H/D 同位素对电荷反转氢键系统的影响：通过多组分计算对 H3XH...YH3 中的三种不同类型（X = C、Si 或 Ge，Y = B、Al 或 Ga）进行系统分类
DOI：
10.1002/jcc.23978
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
T. Udagawa and M. Tachikawa
中科院分区：
文献类型：
--
作者：
Shumpei Yamakawa;Yoshiaki Morino;Masanao Honda and Hiroshi Wada;Enoki Ryosuke;T. Udagawa and M. Tachikawa
利用多组分分子轨道方法的MP2水平，考虑了质子和氘的核量子性质，对9个H3 XH（D）..YH3（X = C，Si，Ge，Y = B，Al，Ga）氢键（HB）体系中3种不同的H/D同位素效应进行了分类.首先，在H_3CH（D）.YH_3（Y = B，Al，or Ge）HB体系中，氘（D）取代引起了常见的H/D几何同位素效应，如共价R（C → H（D））键的收缩和分子间R（H（D）... Y）和R（C... Y）距离的延长。第二，在H_3XH（D）. YH_3（X = Si或Ge，Y = Al或Ge）HB体系中，H原子带负电荷，称为电荷反转氢键（CIHB）体系，D取代导致分子间R（H（D）. Y）和R（X. Y）距离收缩。最后，在H_3XH（D）…BH_3（X = Si或Ge）HB体系中，这些分子间距离R（H（D）…Y）和R（X…Y）也随D取代而收缩，但收缩的起因与CIHB体系不同。分析了H/D同位素效应对原子核相互作用能和波函数空间分布的影响。© 2015威利期刊公司.
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 covalentR(CH(D)) bonds and the elongation of intermolecularR(H(D)…Y) andR(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 intermolecularR(H(D)…Y) andR(X…Y) distances. Finally, in the case of H3XH(D)…BH3(X = Si or Ge) HB systems, these intermolecularR(H(D)…Y) andR(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.