Gyroscopic destabilisation in polyatomic molecules: rotational structure of the low-frequency bending vibrational states ν(23) and ν(11) of dimethylsulfoxide

Arnaud Cuisset; Dmitrií A Sadovskií

doi:10.1063/1.4809738

Gyroscopic destabilisation in polyatomic molecules: rotational structure of the low-frequency bending vibrational states ν(23) and ν(11) of dimethylsulfoxide

J Chem Phys. 2013 Jun 21;138(23):234302. doi: 10.1063/1.4809738.

Authors

Arnaud Cuisset¹, Dmitrií A Sadovskií

Affiliation

¹ Laboratoire de Physico-Chimie de l'Atmosphère, Département de physique, Université du Littoral - Côte d'Opale, 59140 Dunkerque, France. Arnaud.Cuisset@univ-littoral.fr

PMID: 23802955
DOI: 10.1063/1.4809738

Abstract

We give details of the spectroscopic observation of the gyroscopic destabilisation in the ν23 vibrational state of dimethylsulfoxide (DMSO) announced by Cuisset, Pirali, and Sadovskií [Phys. Rev. Lett. 109, 094101 (2012)]. Following the first successful high-resolution spectroscopic study of the rotational structure of the "perpendicular" band of DMSO at 324 cm(-1) associated with the ν23 bending vibrational mode, the rare subsystem of ν23 rotational levels consisting of a series of fourfold quasidegenerate levels (4-clusters) was identified. Our complete analysis of the underlying rotational dynamics uncovered a bifurcation leading to the gyroscopic destabilisation of one of the two stable principal axes of inertia, a phenomenon known previously only in a few triatomic molecules.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Dimethyl Sulfoxide / chemistry*
Models, Molecular*
Quantum Theory*
Vibration

Substances

Dimethyl Sulfoxide