On the nature of highly vibrationally excited states of Thiophosgene

TL;DR

This paper investigates the highly vibrationally excited states of thiophosgene to understand spectral features and mode interactions, employing advanced semiclassical and eigenvalue variation techniques to reveal state localization and potential bifurcations.

Contribution

It introduces combined semiclassical and parametric methods to analyze complex vibrational states and suggests possible bifurcation phenomena in highly excited modes.

Findings

Identification of eigenstate sequences with common localization

Insights into mode mixing and anharmonic Fermi resonances

Indications of bifurcation in out-of-plane bending modes

Abstract

In this work an analysis of the highly vibrationally excited states of thiophosgene (SCCl$_{2}$) is made in order to gain insights into some of the experimental observations and spectral features. The states analyzed herein lie in a spectrally complex region where strong mode mixings are expected due to the overlap of several strong anharmonic Fermi resonances. Two recent techniques, a semiclassical angle space representation of the eigenstates and the parametric variation of the eigenvalues (level-velocities) are used to identify eigenstate sequences exhibiting common localization characteristics. Preliminary results on the influence of highly excited out-of-plane bending modes on the nature of the eigenstates suggest a possible bifurcation in the system.