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非绝热动力学在仿生分子开关光异构化机理中的应用
胡德平
Thesis Advisor兰峥岗 ; 姚礼山
2015-05
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料工程
Keyword光开关 非绝热动力学 Om2/mrci Naip
Abstract光开关是一种对光照敏感的化学物质。由于它们在传感器、自组装以及光照控制等系统中扮演的重要作用,已经被深入研究了很多年。在这些光开关里面,基于E/Z构型异构化的开关在理论与实验领域引起了研究人员们极大的兴趣。一般情况下,这些化合物含有两种或两种以上构型,比如E和Z,它们在光照条件下会相互转化。这种行为在许多生物体内都存在,类似于一个开关的作用。最近研究表明,包括在超快光谱和动力学模拟等情况下,这些光异构化过程会通过势能面交叉点(CIs),也就是说这类反应大都有分子激发态参与其中。因此,要理解这类问题,就必须从激发态层面的光化学反应着手。N-甲基吡咯啉席夫碱(NAIP)由于其光异构化反应类似于视网膜紫质中的生色团,而受到广泛关注。我们在气相条件下用基于OM2/MRCI方法的面跳跃理论,对两种NAIP类模型化合物(OMe-NAIP和dMe-OMe-NAIP)进行了非绝热动力学模拟。两种化合物都通过S0和S1的CI发生了超快的异构化过程。这两种化合物在基态时都有E和Z两种构型,而且被激发之后会发生相互转化。我们发现了两种主要转化通道(CI)α和(CI)β,它们分别在E → Z和Z → E转化过程中起到主要作用。
Other AbstractPhotoswitches are chemicals sensitive to light. They have been studied for several years due to their important roles in sensors, self-assembly and photoinduced biological processes. Recently, photoswitches based on the E/Z isomerization have become of great interest both in theoretical and experimental areas. Generaly, these compounds have two or more configurations, like E and Z, and can be converted to each other after photoabsorption. These behavious exist in many living organisms, analogous to the function of switches. Recently, related studies with ultrafast spectrum and dynamics simulations show that these photoisomerization processes would involve the conical intersections (CIs). In other words, most of these reactions contain the molecular excited states. Thus, to understand these, we should begain with the excited state photochemistry. N-alkylated Indanylidene Pyrroline Schiff Bases (NAIPs) are of great interest because their photoisomerization mimics the primary photoreactions of the retinal chromophore in rhodopsin. The nonadiabatic dynamics of two NAIP models (OMe-NAIP and dMe-OMe-NAIP) in the gas phase are investigated by trajectory surface-hopping method at the semi-empirical OM2/MRCI level. Both molecules show ultrafast isomerization governed by nonadiabatic dynamics via the S0/S1 conical intersections (CIs). Two CIs, CIα and CIβ, play important roles in the E → Z and Z → E isomerization dynamics, respectively.
Department仿真模拟团队
Subject Area理论与计算化学
Date Available2015-07
Subtype硕士 ; 学位论文
Language中文
Document Type学位论文
Identifierhttp://ir.qibebt.ac.cn/handle/337004/8096
Collection蛋白质设计研究组
Affiliation中国科学院青岛生物能源与过程研究所
Recommended Citation
GB/T 7714
胡德平. 非绝热动力学在仿生分子开关光异构化机理中的应用[D]. 北京. 中国科学院大学,2015.
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