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First-Order Interacting Space Approach to Excited-State Molecular Interaction: Solvatochromic Shift of p-Coumaric Acid and Retinal Schiff Base
Journal of Chemical Theory and Computation ( IF 5.5 ) Pub Date : 2018-06-11 00:00:00 , DOI: 10.1021/acs.jctc.7b01089
Kazuma Yanai 1 , Kazuya Ishimura 2 , Akira Nakayama 1 , Jun-ya Hasegawa 1
Affiliation  

A triple-layer QM/sQM/MM method was developed for accurately describing the excited-state molecular interactions between chromophore and the molecular environment (Hasegawa, J.; Yanai, K.; Ishimura, K. ChemPhysChem2015, 16, 305). A first-order-interaction space (FOIS) was defined for the interactions between QM and secondary QM (sQM) regions. Moreover, configuration interaction singles (CIS) and its second-order perturbation theory (PT2) calculations were performed within this space. In this study, numerical implementation of this FOISPT2 method significantly reduced the computing time, which realized application to solvatochromic systems, p-coumaric acid in neutral (p-CA) and anionic forms in aqueous solution, retinal Schiff base in methanol (MeOH) solution, and bacteriorhodopsin (bR). The results were consistent with the experimentally observed absorption spectra of the applied systems. The QM/sQM/MM result for the opsin shift was in better agreement to the experimental result than that of the ordinary QM/MM. A decomposition analysis was performed for the excited-state molecular interactions. Among the electronic interactions, charge-transfer (CT) effect, excitonic interaction, and dispersion interaction showed significant large contributions, while the electronic polarization effect presented only minor contribution. Furthermore, the result was analyzed to determine the contributions from each environmental molecule and was interpreted based on the distance of the molecules from the π system in the chromophores.

中文翻译:

激发态分子相互作用的一阶相互作用空间方法:香豆酸和视网膜席夫碱的溶剂变色位移

所述的三层QM /平方米/ MM方法是为准确地描述的发色团和分子环境(长谷川,J。;柳井,K。;石村,K.之间的激发态的分子相互作用开发ChemPhysChem 201516,305)。为QM和次要QM(sQM)区域之间的交互定义了一阶交互空间(FOIS)。此外,在此空间内执行了配置相互作用单(CIS)及其二阶微扰理论(PT2)的计算。在这项研究中,该FOISPT2方法的数值实现显着减少了计算时间,从而实现了在溶剂化变色体系中的香豆酸(p-香豆酸)的应用。-CA)和阴离子形式存在于水溶液,视网膜席夫碱在甲醇(MeOH)溶液中和细菌视紫红质(bR)中。结果与所应用系统的实验观察吸收光谱一致。与普通QM / MM相比,视蛋白移位的QM / sQM / MM结果与实验结果更好地吻合。对激发态分子相互作用进行分解分析。在电子相互作用中,电荷转移(CT)效应,激子相互作用和色散相互作用表现出显着的巨大贡献,而电子极化效应仅表现出很小的贡献。此外,
更新日期:2018-06-11
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