Involvement of excited triplet state in the photodissociation of cyclobutane |
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| Authors: | Yibo Lei Bingbing Suo Anyang Li Yusheng Dou Yubin Wang Zhenyi Wen |
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| Affiliation: | 1. Bio‐Informatics Institute, Chongqing University of Posts and Telecommunications, Chongqing 400065, People's Republic of China;2. Institute of Modern Physics, Northwest University, Xi'an, Shaanxi 710069, People's Republic of China;3. Department of Physical Sciences, Nicholls State University, PO Box 2022, Thibodaux, LA 70310 |
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| Abstract: | 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 C1? C3 and C2? C4 bond respectively. The singlet‐triplet PECs' intersections have been found in the two breaking C? C bond processes. During the breaking process of the second C2? C4 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 |
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| Keywords: | simulation potential energy curves triplet intermediate MRCISD |
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