期刊
CHEMICAL PHYSICS
卷 452, 期 -, 页码 17-24出版社
ELSEVIER
DOI: 10.1016/j.chemphys.2015.01.009
关键词
Ab initio molecular dynamics; Electronically excited state; Nonadiabatic transition; Zhu-Nakamura version trajectory surface hopping; Sulfuric acid
资金
- Japanese Ministry of Education, Sports, Science and Technology (MEXT), Japan [23224013, 26108511]
- JSPS [26004667]
- Grants-in-Aid for Scientific Research [26108511, 14J04667, 23224013, 26248038] Funding Source: KAKEN
Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S-1 and S-2) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu-Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning's augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO4(1(2)A'') + H(S-2) by S-1-excitation, and (ii) HSO4(2(2)A'') + H(S-2) by S-2-excitation. The direct dissociation dynamics yield products different from the SO2 + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO4 fragment. The trajectories running on S-2 do not hop with S-0 and a nonadiabatic transition happens at the S-2-S-1 conical intersection located at a longer OH bond-length than the S-1-S-0 intersection producing an electronic excited state (2(2)A'') of HSO4 product. (C) 2015 Elsevier B.V. All rights reserved.
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