Molecular vibrations in the presence of velocity-dependent forces

TL;DR

This paper develops a semiclassical theory for molecular vibrations influenced by velocity-dependent forces, such as strong magnetic fields, revealing novel mode couplings and mathematical structures with applications to molecules like H2, HT, and HCN.

Contribution

It introduces a new semiclassical framework for analyzing molecular vibrations under velocity-dependent forces, including magnetic effects, and explores the resulting mode couplings and quadratic eigenvalue problems.

Findings

Identification of vibrational-rotational-translational mode coupling in magnetic fields

Mathematical formulation as a quadratic eigenvalue problem

Numerical examples for H2, HT, and HCN molecules in strong magnetic fields

Abstract

A semiclassical theory of small oscillations is developed for nuclei that are subject to velocity-dependent forces in addition to the usual interatomic forces. When the velocity-dependent forces are due to a strong magnetic field, novel effects arise -- for example, the coupling of vibrational, rotational, and translational modes. The theory is first developed using Newtonian mechanics and we provide a simple quantification of the coupling between these types of modes. We also discuss the mathematical structure of the problem, which turns out to be a quadratic eigenvalue problem rather than a standard eigenvalue problem. The theory is then re-derived using the Hamiltonian formalism, which brings additional insight, including a close analogy to the quantum-mechanical treatment of the problem. Finally, we provide numerical examples for the H$_2$, HT, and HCN molecules in a strong magnetic field.