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Involvement of excited triplet state in the photodissociation of cyclobutane
Author(s) -
Lei Yibo,
Suo Bingbing,
Li Anyang,
Dou Yusheng,
Wang Yubin,
Wen Zhenyi
Publication year - 2007
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21548
Subject(s) - diradical , cyclobutane , singlet state , photodissociation , chemistry , excited state , triplet state , adiabatic process , potential energy , semiclassical physics , ground state , atomic physics , intersystem crossing , quantum , photochemistry , physics , ring (chemistry) , quantum mechanics , organic chemistry
The potential energy curves (PECs) of the ground state and the low‐lying excited states for the photodissociation of cyclobutane have been calculated at the multi‐reference configuration interaction with singlet and doublet excitation (MRCISD) and the multi‐reference second order perturbation theory (MRPT2). Firstly, the PECs are constructed following a reaction path determined by semiclassical dynamics simulation, which suggests that the lowest triplet state of tetramethylene is involved in the photodissociation of cyclobutane. Then, the adiabatic PECs are calculated for the breaking processes of C1C3 and C2C4 bond respectively. The singlet‐triplet PECs' intersections have been found in the two breaking CC bond processes. During the breaking process of the second C2C4 bond, a local minimum has been found on the PEC of the lowest triplet state, which gives us some insight to reinterpret the experimental observed diradical intermediate as being trapped in its triplet state. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008