A quantum chemical study of photochemical processes in the reaction Se + O-2 -> SeO2 with allowance for the spin orbit interaction

作者：Kobzev G I^*; Urvaev D G; Davydov K S; Zaika Yu V

来源：Journal of Structural Chemistry, 2012, 53(1): 12-27.

DOI：10.1134/S0022476612010027

• potential energy surface cross-section
• excited selenium oxocomplexes
• singlet oxygen
• spin-orbit interaction
• zero field splitting parameters

DFT, SA-MCSCF, and MRMP/MCQDPT2 methods in the 6-311++G(2d) basis set are employed to consider the features of the formation reaction of key intermediates (SeOO, Se(O-2)) and photochemical dissociation of selenium dioxide with the formation of singlet oxygen. The cross-sections of potential energy surfaces of SeO2, Se(O-2), and SeOO are constructed and the terms of their ground and excited states are analyzed at the SeOO dissociation limit with regard to spin-orbital interaction. Possible formation channels of O-1(2) ((1)Delta (g) , I-1 pound (g) (+) ) reactive oxygen species during the decay of the excited states of selenium oxocomplexes are revealed. The effect of the spin-orbit interaction on the character of electronic spectrum transitions and zero field splitting in oxygen is estimated.

• 出版日期2012-2