Temperature and isotope effects on water cluster ions with path integral molecular dynamics based on the fourth order Trotter expansion

Abstract

Path integral molecular dynamics simulation based on the fourth order Trotter expansion has been performed to elucidate the geometrical isotope effect of water dimer anions, H(3)O(2)(-), D(3)O(2)(-), and T(3)O(2)(-), at different temperatures from 50 to 600 K. At low temperatures below 200 K the hydrogen-bonded hydrogen nucleus is near the center of two oxygen atoms with mostly O...X...O geometry (where X = H, D, or T), while at high temperatures above 400 K, hydrogen becomes more delocalized, showing the coexistence between O...X-O and O-X...O. The OO distance tends to be shorter as the isotopomer is heavier at low temperatures, while this ordering becomes opposite at high temperatures. It is concluded that the coupling between the OO stretching mode and proton transfer modes is a key to understand such a temperature dependence of a hydrogen-bonded structure.