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Acta Chimica Sinica ›› 2007, Vol. 65 ›› Issue (3): 191-196. Previous Articles Next Articles
Original Articles
林玲, 丁万见, 方维海*, 于建国, 刘若庄*
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通讯作者:
LIN Ling; DING Wan-Jian; FANG Wei-Hai*; YU Jian-Guo; LIU Ruo-Zhuang*
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In the present work, the CASSCF method was employed to optimize structures of thiocamphor in the lowest five electronic states (S0, T1, S1, T2, and S2), which was followed by single-point energy calculations at the MR-CI level. The energy gaps among the S1, T1 and T2 states are very small, but the S2 state is much higher than the T2 state in energy. Similar results were found for other thiocarbonyl compounds. The T1 potential energy profiles of the β-insertion and Norrish II-like reactions were characterized by the B3LYP calculations and the barriers were predicted to be respectively 314.1 and 332.6 kJ/mol with respect to the S0 zero-level. Upon irradiation of thiocamphor at 400 nm, the molecules excited to S1 state do not have enough internal energy to overcome the barrier on the T1 surface. Thus, the internal conversion to the ground state could be the most probable pathway for the S1 deactivation. However, photoexcitation at 254 nm results in the molecules populated in the S2 state. In this case, the system has sufficient internal energy to undergo the β-insertion and Norrish II-like reactions. Indeed, the two reactions have been observed experimentally.
Key words: thiocamphor, photochemistry, ab initio
LIN Ling; DING Wan-Jian; FANG Wei-Hai*; YU Jian-Guo; LIU Ruo-Zhuang*. Theoretical Study on Photochemical Reaction of Thiocamphor[J]. Acta Chimica Sinica, 2007, 65(3): 191-196.
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