Model for vibrationally enhanced tunneling of proton transfer in hydrogen bond

TL;DR

This paper presents a theoretical model analyzing how external vibrations can enhance proton transfer in hydrogen bonds, revealing resonant behaviors and providing a formula for calculating transfer rates, exemplified by the Zundel ion.

Contribution

It introduces an analytic formula for proton transfer rates influenced by external vibrations using a two-dimensional Schrödinger equation framework.

Findings

Resonant peaks in proton transfer rate at specific vibration frequencies.

Symmetric vibration coupling induces rich resonant behavior.

Anti-symmetric and squeezed modes do not produce this resonance.

Abstract

Theoretical analysis of the effect of an external vibration on proton transfer (PT) in a hydrogen bond (HB) is carried out. It is based on the two-dimensional Schr\"odinger equation with trigonometric double-well potential. Its solution obtained within the framework of the standard adiabatic approximation is available. An analytic formula is derived that provides the calculation of PT rate with the help of elements implemented in {\sl {Mathematica}}. We exemplify the general theory by calculating PT rate constant for the intermolecular HB in the Zundel ion ${\rm{H_5O_2^{+}}}$ (oxonium hydrate). This object enables one to explore a wide range of the HB lengths. Below some critical value of the frequency of the external vibration the calculated PT rate yields extremely rich resonant behavior (multiple manifestations of bell-shaped peaks). It takes place at symmetric coupling of the external vibration to the proton coordinate. This phenomenon is absent for anti-symmetric and squeezed mode couplings.