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

R P Brady; S N Yurchenko; G-S Kim; W Somogyi; J Tennyson

doi:10.1039/d2cp03051a

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

Phys Chem Chem Phys. 2022 Oct 12;24(39):24076-24088. doi: 10.1039/d2cp03051a.

Authors

R P Brady¹, S N Yurchenko¹, G-S Kim², W Somogyi¹, J Tennyson¹

Affiliations

¹ Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London, UK. s.yurchenko@ucl.ac.uk.
² Dharma College, Dongguk University, 30, Pildong-ro 1-gil, Jung-gu, Seoul 04620, Korea.

Abstract

We present an ab initio study of the rovibronic spectra of sulphur monoxide (³²S¹⁶O) using internally contracted multireference configuration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets. It covers 13 electronic states X³Σ^-, a¹Δ, b¹Σ⁺, c¹Σ^-, A''³Σ⁺, A'³Δ, A³Π, B³Σ^-, C³Π, d¹Π, e¹Π, C'³Π, and (3)¹Π ranging up to 66 800 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 C³Π-C'³Π and e¹Π-(3)¹Π 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.