Semiclassical molecular dynamics simulations of excited state double-proton transfer in 7-azaindole dimers
Semiclassical molecular dynamics simulations of excited state double-proton transfer in 7-azaindole dimers
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DOI：
10.1063/1.478866
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发表时间：
1999-05-22
影响因子：
4.4
通讯作者：
Miller, WH
中科院分区：
文献类型：
--
作者：
Guallar, V;Batista, VS;Miller, WH
An ab initio excited state potential energy surface is constructed for describing excited state double proton transfer in the tautomerization reaction of photo-excited 7-azaindole dimers, and the ultrafast dynamics is simulated using the semiclassical (SC) initial value representation (IVR). The potential energy surface, determined in a reduced dimensionality, is obtained at the CIS level of quantum chemistry, and an approximate version of the SC-IVR approach is introduced which scales linearly with the number of degrees of freedom of the molecular system. The accuracy of this approximate SC-IVR approach is verified by comparing our semiclassical results with full quantum mechanical calculations. We find that proton transfer usually occurs during the first intermonomer symmetric-stretch vibration, about 100 fs after photoexcitation of the system, and produces an initial 15 percent population decay of the reactant base-pair, which is significantly reduced by isotopic substitution. (C) 1999 American Institute of Physics. [S0021-9606(99)01820-6].
