Nuclear quantum effect and H/D isotope effect on Cl center dot + (H2O)n -> HCl plus OH center dot(H2O)(n-1)(n=1-3) reactions

作者：Sugiura Keita; Tachikawa Masanori; Udagawa Taro^*

来源：RSC Advances, 2018, 8(31): 17191-17201.

DOI：10.1039/c8ra02679c

Cl center dot + (H2O)(n) -> HCl + OH center dot(H2O)(n-1)(n = 1-3) reactions are fundamental and important ones in atmospheric chemistry. In this study, we focused on the nuclear quantum effect (NQE) of the hydrogen nucleus on these reactions with the aid of the multicomponent quantum mechanics (MC_QM) method, which can directly take account of NQE of light nuclei. Our study reveals that the NQE of the hydrogen nucleus lowers the activation barriers of the reactions and enhances the catalytic effects of second and third water molecules. In particular, we find that (i) the NQE of the proton removes the activation barrier of the reverse reaction of HCl + OH center dot -> Cl center dot + H2O, and (ii) the catalytic effect of the third water molecule appears in only our MC_QM calculation. We also analyze the H/D isotope effects on these reactions by using the MC_QM method.

• 出版日期2018