空间挤迫型多烯类光驱动分子转动马达的理论研究与设计

项目名称： 空间挤迫型多烯类光驱动分子转动马达的理论研究与设计

项目编号： No.21473107

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 刘峰毅

作者单位： 陕西师范大学

项目金额： 84万元

中文摘要： 空间挤迫型多烯类分子转动马达是一类极具应用前景的光驱动分子马达。深刻理解该类马达背后的光化学和光物理本质，是实现优化马达性能、改进能量转换效率以及设计新型光驱动马达等目标的关键。本项目拟从几个典型多烯分子转动马达入手，采用多参考态从头算方法系统研究它们的光致顺反异构化反应，探索其基态和激发态势能面，确定非绝热光化学反应路径；在此基础上确立分子马达的物理学参量（如旋转驱动力、转动方向、转速等）与化学反应机理的量子化学描述间的联系，阐明多烯类光驱动分子马达的工作机理；寻找影响其旋转方向性、旋转速度和能量转化效率的关键因素，并通过化学修饰、改变环境等手段调控其光化学反应途径；最终尝试性开展新型转动马达的设计，探索分子马达在化学和材料科学领域的新应用。上述研究结果将对分子马达的设计、合成及应用提供理论指导。

中文关键词： 量子化学计算；反应机理；电子激发态；光化学；分子马达

英文摘要： Light-driven molecular rotary motors based on overcrowded alkenes have shown great potential for a variety of applications. In order to improve the performance, enhance energy conversion efficiency and design novel light-driven molecular devices, deep understandings of the photochemistry and photophysics behind these motors are prerequisites. However, their high-level theoretical treatment has been a challenging topic for long. In the current proposal, we will employ multireference ab initio methods to systematically study several typical alkene-based rotary motor systems. The Z-E photoisomerization process of these alkenes will be investigated, their ground- and excited-state PESs will be explored and nonadiabatic photochemical reaction channels will be uncovered. On top of these findings, the connection between the quantum-chemistry descriptions of the photochemical reaction and the physics of the rotary motor (such as driving force, directionality and speed of rotation, etc.) will be established, followed by the working mechanism of the motors being rationalized. We also aim to find the critical geometrical and electronic factors which control the direction of rotation, speed of rotation as well as the energy conversion efficiency, so as to tune the photochemical reaction path, by modifying structure and/or changing surrounding environment. Ultimately, we attempt to design new type of light-driven molecular rotary motor, and find their new applications in chemistry and material sciences. The findings of the current project will provide theoretical guidelines for the design, synthesis and application of light-driven molecular rotary motor.

英文关键词： Quantum chemistry calculation;Reaction mechanism;Electronic excited state;Photochemistry;Molecular motor