Affiliation:
1. Department of Chemical Physics Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) University of Science and Technology of China Hefei 230026 China
2. Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China
3. Hefei National Laboratory University of Science and Technology of China Hefei 230088 China
Abstract
AbstractHydrogen isotopic effect, as the key to revealing the origin of Earth's water, arises from the H/D mass difference and quantum dynamics at the transition state of reaction. The ion‐molecule charge‐exchange reaction between water (H2O/D2O) and argon ion (Ar+) proceeds spontaneously and promptly, where there is no transition‐state or intermediate complex. In this energetically resonant process, we find an inverse kinetic isotope effect (KIE) leading to the higher charge transfer rate for D2O, by the velocity map imaging measurements of H2O+/D2O+ products. Using the average dipole orientation capture model, we estimate the orientation angles of C2v axis of H2O/D2O relative to the Ar+ approaching direction and attribute to the difference of stereodynamics. According to the long‐distance Landau‐Zener charge transfer model, this inverse KIE could be also attributed to the density‐of‐state difference of molecular bending motion between H2O+ and D2O+ around the resonant charge transfer.
Funder
National Natural Science Foundation of China