Photochromic Mechanism of a Bridged Diarylethene: Combined Electronic Structure Calculations and Nonadiabatic Dynamics Simulations

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• 作者：Ya-Ting Wang ; Yuan-Jun Gao ; Qian Wang ; Ganglong Cui
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：February 2, 2017
• 年：2017
• 卷：121
• 期：4
• 页码：793-802
• 全文大小：641K
• ISSN：1520-5215

文摘

Intramolecularly bridged diarylethenes exhibit improved photocyclization quantum yields because the anti-syn isomerization that originally suppresses photocyclization in classical diarylethenes is blocked. Experimentally, three possible channels have been proposed to interpret experimental observation, but many details of photochromic mechanism remain ambiguous. In this work we have employed a series of electronic structure methods (OM2/MRCI, DFT, TDDFT, RI-CC2, DFT/MRCI, and CASPT2) to comprehensively study excited state properties, photocyclization, and photoreversion dynamics of 1,2-dicyano[2,2]metacyclophan-1-ene. On the basis of optimized stationary points and minimum-energy conical intersections, we have refined experimentally proposed photochromic mechanism. Only an S₁/S₀ minimum-energy conical intersection is located; thus, we can exclude the third channel experimentally proposed. In addition, we find that both photocyclization and photoreversion processes use the same S₁/S₀ conical intersection to decay the S₁ system to the S₀ state, so we can unify the remaining two channels into one. These new insights are verified by our OM2/MRCI nonadiabatic dynamics simulations. The S₁ excited-state lifetimes of photocyclization and photoreversion are estimated to be 349 and 453 fs, respectively, which are close to experimentally measured values: 240 ± 60 and 250 fs in acetonitrile solution. The present study not only interprets experimental observations and refines previously proposed mechanism but also provides new physical insights that are valuable for future experiments.