O-loss photodissociation of the OCS+ ion in the low-lying electronic states studied using multiconfiguration second-order perturbation theory

✍ Scribed by Hua Dong; Bo-Zhen Chen; Ming-Bao Huang; Hai-Bo Chang

• Book ID: 104577068
• Publisher: John Wiley and Sons
• Year: 2010
• Tongue: English
• Weight: 453 KB
• Volume: 111
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.22903

✦ Synopsis

Abstract

The CASPT2 potential energy curves (PECs) for O‐loss dissociation from the X^2^Π, A^2^Π, B^2^Σ^+^, C^2^Σ^+^, 1^4^Σ^−^, 1^2^Σ^−^, and 1^4^Π states of the OCS^+^ ion were calculated. The PEC calculations indicate that X^2^Π, 1^4^Σ^−^, 1^2^Σ^−^, and 1^4^Π correlate with CS^+^(X^2^Σ^+^) + O(^3^P~g~); A^2^Π and B^2^Σ^+^ correlate with CS^+^(A^2^Π) + O(^3^P~g~); and C^2^Σ^+^ probably correlates with CS^+^(X^2^Σ^+^) + O(^1^D~g~). The CASSCF minimum energy crossing point (MECP) calculations were performed for the C^2^Σ^+^/1^4^Σ^−^, C^2^Σ^+^/1^4^Π, A^2^Π/1^4^Σ^−^, A^2^Π/1^2^Σ^−^, A^2^Π/1^4^Π, and B^2^Σ^+^/1^2^Σ^−^ state pairs and the spin‐obit couplings were calculated at the located MECPs. A conical intersection point between the B^2^Σ^+^ and C^2^Σ^+^ potential energy surfaces was found at the CASSCF level. Based on our calculations, seven O‐loss predissociation processes of the C^2^Σ^+^ state are suggested and an appearance potential value of 7.13 eV for the CS^+^ + O product group is predicted. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011