Eigenstates of Thiophosgene Near the Dissociation Threshold -- Deviations From Ergodicity

TL;DR

This study investigates highly excited eigenstates of thiophosgene near the dissociation threshold, revealing localized states that challenge the assumption of statistical energy distribution at high excitation levels.

Contribution

It provides new insights into quantum ergodicity deviations in thiophosgene's eigenstates, highlighting nonstatistical vibrational energy flow at high energies.

Findings

Presence of localized eigenstates near dissociation threshold

Evidence of nonstatistical vibrational energy flow

Correlation with sharp spectral features in experiments

Abstract

A subset of the highly excited eigenstates of thiophosgene (SCCl$_{2}$) near the dissociation threshold are analyzed using sensitive measures of quantum ergodicity. We find several localized eigenstates, suggesting that the intramolecular vibrational energy flow dynamics is nonstatistical even at such high levels of excitations. The results are consistent with recent observations of sharp spectral features in the stimulated emission spectra of SCCl$_{2}$