The role of πσ* states in the photochemistry of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane†
The role of πσ* states in the photochemistry of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane†
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πσ* 态在手性氟乙烯衍生物 (4-甲基亚环己基) 氟甲烷光化学中的作用†
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发表时间：
2011
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通讯作者：
L. González
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作者：
D. Kinzel;J. González;L. González
对手性氟代乙烯衍生物（4-甲基环己叉基）氟甲烷的激发态和势能曲线进行了多构型从头计算，证明了πσ* 态在萃取HF中起着重要作用.我们发现，要正确描述标题分子在激发到明亮价态ππ* 时的弛豫，需要的不仅仅是基态和价态ππ *.在FC几何构型下，发现了πσ* 和ππ* 态之间的一个圆锥形交叉点，这使得HF在电子激发态的解离成为可能。这一结论不同于以往对烯键式体系的研究，其中解离被假定为基态反应。© 2011 Wiley Periodicals，Inc. Int J Quantum Chem 111：3394-3404，2011
Multiconfigurational ab initio calculations of the excited states and potential energy curves of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane provide evidence that πσ* states play an important role in the abstraction of HF. We show that more than the ground and valence ππ* states are necessary to correctly describe the relaxation of the title molecule upon excitation to the bright valence ππ* state. A conical intersection between the πσ* and ππ* states has been identified at the FC geometry which makes dissociation of HF in the electronic excited state possible. This conclusion is different from all the previous studies on ethylenic systems where dissociation is postulated as a ground state reaction. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111:3394–3404, 2011