苯酚光解离动力学的全维多态半经典的轨迹模拟研究
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- 英文论文题名：Full-Dimensional Multistate Semiclassical Trajectory Simulations for Photodissociation Dynamics of Phenol
- 论文作者：许雪飞 ; 郑晶晶 ; 阳科 ; Donald G.Truhlar
- 英文论文作者：Xuefei Xu(X.Xu) ; Jingjing Zheng(J.Zheng) ; Donald G.Truhlar(D.G.Truhlar) ; Center for Combustion Energy ; Tsinghua University ; Department of Chemistry ; Chemical Theory Center ; and Supercomputing Institute ; University of Minnesota
- 年：2016
- 作者机构：清华大学燃烧能源中心;Department of Chemistry,Chemical Theory Center,and Supercomputing Institute,University of Minnesota;
- 论文关键词：苯酚光解离 ; 非绝热动力学 ; 全维轨迹模拟
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十九分会：化学中的量子与经典动力学
- 语种：中文
- 分类号：O625.312;O644.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十九分会 ; 化学中的量子与经典动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：218k
- 原文格式：D
- 会议级别：全国
摘要
生命的基本组成单元核酸碱基和氨基酸等分子自身具有一定的光稳定特性,使之可以对抗一定程度的UV辐射。其机制在于此类分子的激发态可通过超快的非辐射弛豫通道迅速返回到分子的基态。苯酚分子作为氨基酸分子酪氨酸的模型分子,其光解离生成H原子和苯氧自由基的非绝热动力学过程一直是实验和理论研究的重点。我们通过结合四种理论方法,(1)基于组态平滑的4-fold way透热化方法,(2)实现多态全维势能面拟合的锚点反应势方法,(3)同时考虑相干和去相干的CSDM多态轨迹模拟方法,和(4)在经典轨迹模拟中引入量子隧穿效应的行军蚁算法,实现了对苯酚光解离非绝热动力学过程的全维(33维)多态轨迹模拟。通过对最终态的解析,再现了实验上观测到的动能释放光谱,并获得了大量实验上无法直接获得的信息。
Building blocks of life, nucleic acid bases and amino acids, have an inherent photostability against UV irradiation. The mechanism of "photostability" is due to the existence of ultrafast non-radiative decay routes from their excited states to ground states. Phenol is a model molecule of the amino acid molecule, tyrosine, and its photodissociation dynamics to H and phenoxyl radical have been studied extensively. We did full-dimensional multistate semiclassical trajectory simulations for this nonadiabatic process by combining four theoretical methods, which are the 4-fold way diabatization method based on the configurational smoothness, anchor points reactive potential for fitting of full-dimensional potential energy surfaces for multistates, CSDM multistate trajectory simulation method considering both coherence and decoherence, and army ants tunneling to including tunneling in classical simulations. By analyzing the final states, the simulations reproduced experimental total kinetic energy release spectra and reveal a lot of details that cannot be directly obtained by experiments.
Building blocks of life, nucleic acid bases and amino acids, have an inherent photostability against UV irradiation. The mechanism of "photostability" is due to the existence of ultrafast non-radiative decay routes from their excited states to ground states. Phenol is a model molecule of the amino acid molecule, tyrosine, and its photodissociation dynamics to H and phenoxyl radical have been studied extensively. We did full-dimensional multistate semiclassical trajectory simulations for this nonadiabatic process by combining four theoretical methods, which are the 4-fold way diabatization method based on the configurational smoothness, anchor points reactive potential for fitting of full-dimensional potential energy surfaces for multistates, CSDM multistate trajectory simulation method considering both coherence and decoherence, and army ants tunneling to including tunneling in classical simulations. By analyzing the final states, the simulations reproduced experimental total kinetic energy release spectra and reveal a lot of details that cannot be directly obtained by experiments.
引文
[1]Xu,X.;Zheng,J.;Yang,K.R.;Truhlar,D.G.,J.Am.Chem.Soc.2014,136:16378.
[2]Yang,K.R.;Xu,X.;Zheng,J.;Truhlar,D.G.Chem.Sci.2014,5:4661.
[2]Yang,K.R.;Xu,X.;Zheng,J.;Truhlar,D.G.Chem.Sci.2014,5:4661.