An ab initio study of the rovibronic spectrum of sulphur monoxide (SO): diabatic vs. adiabatic representation. Issue 39 (29th September 2022)

• Record Type: Journal Article
• Authors: Brady, R. P.; Yurchenko, S. N.; Kim, G.-S.; Somogyi, W.; Tennyson, J.
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 39(2022)
• Page Start: 24076
• Page End: 24088
• Publication Date: 2022-09-29
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp03051a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We present an ab initio study of the rovibronic spectra of sulphur monoxide ( 32 S 16 O) using internally contracted multireference configuration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets where non-adiabatic effects are treated. Abstract : We present an ab initio study of the rovibronic spectra of sulphur monoxide ( 32 S 16 O) using internally contracted multireference configuration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets. It covers 13 electronic states X 3 Σ −, a 1 Δ, b 1 Σ +, c 1 Σ −, A′′ 3 Σ +, A′ 3 Δ, A 3 Π, B 3 Σ −, C 3 Π, d 1 Π, e 1 Π, C′ 3 Π, and (3) 1 Π 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 C 3 Π–C′ 3 Π and e 1 Π–(3) 1 Π 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.