An ab initio study of the rovibronic spectrum of sulphur monoxide (SO): diabatic vs. adiabatic representation

TL;DR

This study provides a comprehensive ab initio spectroscopic model of sulfur monoxide (SO), including potential energy, dipole, and coupling curves, with a focus on diabatic versus adiabatic representations, covering a broad spectral range.

Contribution

It introduces a fully reproducible ab initio model of SO's rovibronic spectrum, incorporating diabatic and adiabatic representations with detailed coupling data.

Findings

Constructed 13 potential energy curves for SO

Developed a property-based diabatisation method for avoided crossings

Produced the first fully reproducible spectroscopic model of SO

Abstract

We present an ab initio study of the rovibronic spectra of sulfur monoxide ($^{32}$S$^{16}$O) using internally contracted multireference confoguration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets. It covers 13 electronic states $X^{3}\Sigma^{-}$, $a^{1}\Delta$, $b^{1}\Sigma^{+}$, $c^{1}\Sigma^{-}$, $A^{\prime\prime 3}\Sigma^{+}$, $A^{\prime 3}\Delta$, $A^{3}\Pi$, $B^{3}\Sigma^{-}$, $C^{3}\Pi$, $d^{1}\Pi$, $e^{1}\Pi$, $C^{\prime 3}\Pi$, and $(3)^{1}\Pi$ ranging up to 66800 cm$^{-1}$. The ab initio spectroscopic model includes 13 potential energy curves, 23 dipole and transition dipole moment curves, 23 spin-orbit curves, and 14 electronic angular momentum curves. A diabatic representation is built by removing the avoided crossings between the spatially degenerate pairs $C^{3}\Pi - C^{\prime 3}\Pi$ and $e^{1}\Pi - (3)^{1}\Pi$ through a property-based diabatisation method. We also present non-adiabatic couplings and diabatic couplings for these avoided crossing systems. All phases for our coupling curves are defined, and consistent, providing the first fully reproducible spectroscopic model of SO covering the wavelength range longer than 147 nm. Finally, an ab initio rovibronic spectrum of SO is computed.