Molecular vibrations in the presence of velocity-dependent forces
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, HT, and HCN molecules in a strong magnetic field.
Keywords
Cite
@article{arxiv.2212.10246,
title = {Molecular vibrations in the presence of velocity-dependent forces},
author = {Erik Tellgren and Tanner Culpitt and Laurens Peters and Trygve Helgaker},
journal= {arXiv preprint arXiv:2212.10246},
year = {2023}
}