Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor | |
A. Kazaryan Z. Lan; L. Schaefer; W. Thiel; M. Filatov, | |
2011 | |
发表期刊 | J. Chem. Theo. Compt. |
卷号 | 7期号:1页码:2189-2199 |
摘要 | We report a theoretical study of the photoisomerization step in the operating cycle of a prototypical fluorene-based molecular rotary motor (1). The potential energy surfaces of the ground electronic state (S0) and the first singlet excited state (S1) are explored by semiempirical quantum-chemical calculations using the orthogonalization-corrected OM2 Hamiltonian in combination with a multireference configuration interaction (MRCI) treatment. The OM2/MRCI results for the S0 and S1 minima of the relevant 1-P and 1-Misomers and for the corresponding S0 transition state are in good agreement with higher-level calculations, both with regard to geometries and energetics. The S1 surface is characterized at the OM2/MRCI level by locating two S0–S1 minimum-energy conical intersections and nearby points on the intersection seam and by computing energy profiles for pathways toward these MECIs. Semiclassical Tully-type trajectory surface hopping (TSH) simulations with on-the-fly OM2/MRCI calculations are carried out to study the excited-state dynamics after photoexcitation to the S1 state. Fast relaxation to the ground state is observed through the conical intersection regions, predominantly through the lowest-energy one with a strongly twisted central C═C double bond and pyramidalized central carbon atom. The excited-state lifetimes for the direct and inverse photoisomerization reactions (1.40 and 1.79 ps) and the photostationary state ratio (2.7:1) from the TSH-OM2 simulations are in good agreement with the available experimental data (ca. 1.7 ps and 3:1). Excited-state lifetimes, photostationary state ratio, and dynamical details of the TSH-OM2 simulations also agree with classical molecular dynamics simulations using a reparametrized optimized potentials for liquid simulations (OPLS) all-atom force field with ad-hoc surface hops at predefined conical intersection points. The latter approach allows for a more extensive statistical sampling. |
学科领域 | 仿真与模拟 |
文献类型 | 期刊论文 |
条目标识符 | http://ir.qibebt.ac.cn/handle/337004/1331 |
专题 | 蛋白质设计研究组 |
推荐引用方式 GB/T 7714 | A. Kazaryan Z. Lan,L. Schaefer,W. Thiel,et al. Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor[J]. J. Chem. Theo. Compt.,2011,7(1):2189-2199. |
APA | A. Kazaryan Z. Lan,L. Schaefer,W. Thiel,&M. Filatov,.(2011).Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor.J. Chem. Theo. Compt.,7(1),2189-2199. |
MLA | A. Kazaryan Z. Lan,et al."Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor".J. Chem. Theo. Compt. 7.1(2011):2189-2199. |
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