Stable configuration of a molecule as spontaneous symmetry breaking

TL;DR

This paper explores the symmetry properties of molecular potentials, demonstrating that molecules inherently possess at least one symmetric vibrational mode, and provides methods to analyze molecular shapes and vibrational frequencies using symmetry principles.

Contribution

It introduces a group of symmetry transformations for molecular potentials, derives fundamental formulas for normal modes, and applies symmetry analysis to predict vibrational properties and molecular shapes.

Findings

Every molecule has at least one totally symmetric normal mode.

Symmetry analysis can predict vibrational frequency magnitudes.

Application of symmetry theorems to molecular shape analysis.

Abstract

In a molecule subjected to no external fields, motion of nuclei is governed by a function V of nuclear coordinates. This function (potential energy) is a sum of two terms: Coulomb repulsion between nuclei and the electronic effective potential E which results from the Born-Oppenheimer approximation. In this paper we have presented a group of coordinate transformations which are the symmetries of functions E and V. We showed that the formula for dynamical representation, which has fundamental importance in the symmetry analysis of normal modes of a molecule, follows from these symmetries. In addition, we proved that every molecule has at least one normal mode belonging to the totally symmetric (and therefore Raman-active) irreducible representation of the point group of that molecule. Next, we used symmetries of V and E to analyze possible shapes of some molecule types. We applied both Abud-Sartori-Michel theorem and symmetry adapted expansion of the electronic effective potential around united atom. Finally, we derived an approximate relation which predicts order of magnitude of the vibration frequency from the bond length in a diatomic molecule.