Ab Initio Study of Decay Dynamics of 1-Nitronaphthalene Initiated from the S2(ππ* + nNOπ*) State

被引:5
作者
Yang, Meng [1 ]
Zhang, Tengshuo [1 ]
Xue, Jiadan [1 ]
Zheng, Xuming [1 ]
机构
[1] Zhejiang Sci Tech Univ, Dept Chem, Hangzhou 310018, Zhejiang, Peoples R China
基金
中国国家自然科学基金;
关键词
MULTIREFERENCE PERTURBATION-THEORY; AROMATIC-HYDROCARBONS; TRIPLET MANIFOLD; STATE; PHOTOCHEMISTRY; RAMAN; PHOTOLYSIS; CASSCF; PHOTOPHYSICS; ABSORPTION;
D O I
10.1021/acs.jpca.7b11003
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Irradiation of nitro-PAHs in solution at ambient conditions leads to formation of its lowest excited triplet, dissociation intermediates nitrogen oxide (NO center dot) and aryloxy radical (Ar-O-center dot). Experimental and theoretical studies demonstrated that Franck-Condon excited singlet state S-FC(pi pi*) to a receiver, higher-energy triplet state T-n(n pi*) controlled the ultrafast population of the triplet state and, hence, the slight fluorescence yield of nitronaphthalenes. However, the detailed information about the curve crossings of potential energy surfaces and the major channels for forming T-1 species and Ar-O-center dot radical were unclear. Here, by using the CASSCF//CASPT2 method, an efficient decay channel is revealed: S2-FC-1NN -> S2-MIN-1NN -> or S2T3-MIN-1NN -> T3-MIN-1NN or T3T2-MIN-1NN -> T2-MIN-1NN or T2T1-MIN-1NN -> T1-MIN-1NN. This explains the high yield of T1-1NN species and minor yield of Ar-O-center dot and NO center dot radicals. The calculation results suggest the bifurcation processes take place predominantly after the internal conversion to the T1-1NN state via T2T1-MIN-1NN one leads to T1-MIN-1NN, while the other to T1-MIN-ISO to produce Ar-O-center dot and NO center dot radicals.
引用
收藏
页码:2732 / 2738
页数:7
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