Calculation of IR absorption intensities for hydrogen bond from exactly solvable Schr\"odinger equation

TL;DR

This paper develops a theoretical model for IR absorption in hydrogen bonds using an exactly solvable Schrödinger equation with a double-well potential, applied specifically to the Zundel ion, to predict spectral intensities.

Contribution

It introduces an exact analytical solution for IR spectra of hydrogen bonds based on a trigonometric double-well potential and extends it to two-dimensional cases with heavy atom excitation.

Findings

Calculated IR absorption intensities for the Zundel ion

Demonstrated the applicability of the exact solution to hydrogen bonds

Provided a framework for analyzing IR spectra with analytical methods

Abstract

A theoretical description of IR spectroscopy data for a hydrogen bond (HB) is constructed on the base of trigonometric double-well potential for which an exact analytic solution of the one-dimensional Schr\"odinger equation (SE) is available. The wave functions (full orthogonal basis) are expressed via the spheroidal function while its spectrum of eigenvalues yields the corresponding energy levels (both special functions are implemented in {\sl {Mathematica}}). Then an approximate solution of two-dimensional SE taking into account the excitation state of heavy atoms stretching mode in HB is obtained. It is constructed by decomposing over the above mentioned basis within the framework of standard adiabatic separating the proton motion from that of the heavy atoms. We exemplify the general theory by calculating the IR relative absorption intensities for HB in the Zundel ion ${\rm{H_5O_2^{+}}}$ (oxonium hydrate).