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	Role of the (3)(pi pi*) State in Photolysis of Lumisantonin: Insight from ab Initio Studies
	Chen, Xing ; Rinkevicius, Zilvinas（Royal Inst Technol, Sch Biotechnol） ; Luo, Yi（Royal Inst Technol, Sch Biotechnol） ; Agren, Hans（Royal Inst Technol, Sch Biotechnol） ; Cao, Zexing ; Cao ZX(曹泽星)
	2011-05-31
英文摘要	The CASSCF and CASPT2 methodologies have been used to explore the potential energy surfaces of lumisantonin in the ground and low-lying triplet states along the photoisomerization pathways. Calculations indicate that the (n pi*) state is the accessible low-lying singlet state with a notable oscillator strength under an excitation wavelength of 320 nm and that it can effectively decay to the (3)(pi pi*) state through intersystem crossing in the region of minimum surface crossings with a notable spin-orbital coupling constant. The 3(pi pi*) state, derived from the promotion of an electron from the pi-type orbital mixed with the sigma orbital localized on the C-C bond in the three-membered alkyl ring to the pi* orbital of conjugation carbon atoms, plays a critical role in C-C bond cleavage. Based on the different C-C bond rupture patterns, the reaction pathways can be divided into paths A and B. Photolysis along path A arising from C1-C5 bond rupture is favorable because of the dynamic and thermodynamic preferences on the triplet excited-state PES. Path B is derived from the cleavage of the C5-C6 bond, leading first to a relatively stable species, compared to intermediate A-INT formed on the ground state PES. path B is relatively facile for the pyrolytic reaction. The present results provide a basis to interpret the experimental observations.; Swedish Infrastructure Committee (SNIC)[SNIC 022/09-25]; National Science Foundation of China[20733002, 20873105]; Ministry of Science and Technology[2011CB808504]
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://dx.doi.org/doi:10.1021/jp203369b]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Chen, Xing,Rinkevicius, Zilvinas,Luo, Yi,et al. Role of the (3)(pi pi*) State in Photolysis of Lumisantonin: Insight from ab Initio Studies[J],2011.
APA	Chen, Xing,Rinkevicius, Zilvinas,Luo, Yi,Agren, Hans,Cao, Zexing,&曹泽星.(2011).Role of the (3)(pi pi*) State in Photolysis of Lumisantonin: Insight from ab Initio Studies..
MLA	Chen, Xing,et al."Role of the (3)(pi pi*) State in Photolysis of Lumisantonin: Insight from ab Initio Studies".(2011).

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