Schr\"odinger equation with Pauli-Fierz Hamiltonian and double well potential as model of vibrationally enhanced tunneling for proton transfer in hydrogen bond

TL;DR

This paper develops an analytical solution to the vibrationally enhanced proton tunneling in hydrogen bonds using a two-dimensional Schrödinger equation with a Pauli-Fierz Hamiltonian and double-well potential, relevant for polariton chemistry and enzymatic processes.

Contribution

It introduces a first-order adiabatic approximation solution for the Pauli-Fierz Hamiltonian in a double-well potential, specifically applied to proton transfer in hydrogen bonds.

Findings

Vibrational strong coupling significantly enhances proton transfer rates.

The derived formula accurately predicts rate constants for the Zundel ion.

Resonant activation effect remains stable across different vibrational modes.

Abstract

A solution of the two-dimensional Schr\"odinger equation with Pauli-Fierz Hamiltonian and trigonometric double-well potential is obtained within the framework of the first-order of adiabatic approximation. The case of vibrational strong coupling is considered which is pertinent for polariton chemistry and (presumably) for enzymatic hydrogen transfer. We exemplify the application of the solution by calculating the proton transfer rate constant in the hydrogen bond of the Zundel ion ${\rm{H_5O_2^{+}}}$ (oxonium hydrate) within the framework of the Weiner's theory. An analytic formula is derived which provides the calculation of the proton transfer rate with the help of elements implemented in {\sl {Mathematica}}. The parameters of the model for the Zundel ion are extracted from the literature data on IR spectroscopy and quantum chemical calculations. The approach yields a vivid manifestation of the phenomenon of vibrationally enhanced tunneling, i.e., a sharp bell-shaped peak of the rate enhancement by the external vibration at its symmetric coupling to the proton coordinate. The results obtained testify that the effect of resonant activation in our model is robust and stable to variations in the types of the quadratically coupled mode (vibrational strong coupling or symmetric one).