A Global Algebraic Treatment for XY2 Molecules : Application to D2S

TL;DR

This paper develops a comprehensive algebraic framework for analyzing XY2 molecules, particularly D2S, using group theoretical methods to accurately reproduce experimental vibrational spectra up to dissociation.

Contribution

It introduces a unified algebraic formalism combining u(2) and u(3) chains for vibrational modes, enabling precise modeling of stretch-bend interactions in XY2 molecules.

Findings

Successfully reproduces experimental data for D2S

Provides explicit operators for stretch-bend interactions

Demonstrates the formalism's effectiveness up to dissociation limit

Abstract

We suggest to use for $XY_2$ molecules some results previously established in a series of articles for vibrational modes and electronic states with an $E$ symmetry type. We first summarize the formalism for the standard $u(2)\supset su(2)\supset so(2)$ chain which, for its most part, can be kept for the study of both stretching and bending modes of $XY_2$ molecules. Next the also standard chain $u(3)\supset u(2) \supset su(2) \supset so(2)$ which is necessary, within the considered approach, is introduced for the stretching modes. All operators acting within the irreducible representation (\textit{irrep}) $[N00]\equiv [N\dot{0}]$ of $u(3)$ are built and their matrix elements computed within the standard basis. All stretch-bend interaction operators taking into account the polyad structure associated with a resonance $\omega_1\approx \omega_3 \approx 2 \omega_2$ are obtained. As an illustration, an application to the $D_2S$ molecular system is considered, especially the symmetrization in $C_{2v}$. It is shown that our unitary formalism allows to reproduce in an extremely satisfactory way all the experimental data up to the dissociation limit.