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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >On the light-driven isomerization of a model asymmetric molecular rotor: Conformations and conical intersections of 2-cyclopentylidene-tetrahydrofuran
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On the light-driven isomerization of a model asymmetric molecular rotor: Conformations and conical intersections of 2-cyclopentylidene-tetrahydrofuran

机译：关于模型不对称分子转子的光驱动异构化：2-环戊叉基-四氢呋喃的构型和圆锥形交点

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摘要

The ground state potential energy surface of the model molecular rotor 2-cyclopentylidene-tetrahydrofuran (CPTHF) has been characterized by calculating minimum energy conformations, racemization pathways, and rotational barriers with high level ab initio electronic structure calculations. Two conformers with their corresponding enantiomers are found. The activation barriers for racemization are negligible, therefore thermal racemization takes place at room temperature. Torsional transition states, calculated using multiconfigurational CASSCF calculations, show twisted and pyramidalized biradical structures. Additionally, the photochemistry of CPTHF has been investigated using the accurate MS-CASPT2/CASSCF methodology. In the UV spectrum it is found that the spectroscopic state is the S_1, which corresponds to a ππ* transition within the ethylene moiety. To understand light-triggered isomerization around the C - C bond, five conical intersections between the S_0 and S_1 have been located for each conformer of CPTHF, which allow the system to rapidly decay to the electronic ground state.
机译：模型分子转子2-环戊叉基-四氢呋喃（CPTHF）的基态势能面已通过从头算电子结构计算得出的最小能量构象，消旋路径和旋转势垒得到了表征。发现两个构象体及其相应的对映体。外消旋作用的激活障碍可以忽略不计，因此热消旋作用在室温下发生。使用多配置CASSCF计算得出的扭转过渡状态显示了扭曲和金字塔形的双自由基结构。此外，已经使用精确的MS-CASPT2 / CASSCF方法研究了CPTHF的光化学。在UV光谱中，发现光谱状态为S_1，其对应于乙烯部分内的ππ*跃迁。为了了解C-C键周围的光触发异构化，已经为CPTHF的每个构象体在S_0和S_1之间定位了五个圆锥形交叉点，这使系统可以快速衰减到电子基态。

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