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State to State Photodissociation Dynamics of Vibrationally Excited D2O in B Band
Shan-yu Han,Lin-sen Zhou,Dai-qian Xie*
Author NameAffiliationE-mail
Shan-yu Han Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China  
Lin-sen Zhou Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China  
Dai-qian Xie* Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, ChinaSynergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei 230026, China dqxie@nju.edu.cn 
Abstract:
The state-to-state photodissociassion dynamics for the B band of D2O have been explored from quantum dynamical calculations including the electronic ~X and ~B states. The calculations were carried out using a Chebyshev real wave packet method. The calculated absorption spectra, product state distributions, and branching ratios from different initial vibrational states show di?erent dynamic features, due to the different shapes of the vibrational wavefunctions. The initial bending mode (0,1,0) generates two lobes with a shallow minimum on the absorption spectrum and a slight inverted vibrational population of OD(~X ) product at high total energies. The rotational state distributions of OD(~X , v=0) product are highly inverted and depend weakly on the initial state and total energy. On the other hand, the ro-vibrational distributions of OD(A~) product strongly oscillate with the total energy, which are dominated by the long-living resonances and depend sensitively on the potential surfaces. The antisymmetric stretching mode (0,0,1) has large OD( ~ A)/OD(~X ) branching ratios at high total energies, which indicates that the B band dissociation proceeds mainly via the adiabatic pathway in some cases.
Key words:  Photodissociation, D2O, Vibrationally excited state, Conical intersection, Quantum dynamics
FundProject:
不同初始振动态下D2O在B带的态-态光解动力学
韩山雨,周林森,谢代前*
摘要:
利用高精度的非绝热从头算势能面,采用量子实波包方法研究了D2O在3个不同初始振动态(0,1,0)、(1,0,0)和(0,0,1)下光激发到~B态解离过程的态-态量子动力学.结果表明,由于初始振动波函数的形状不同,从不同振动态产生的吸收光谱、产物分布和产物分支比具有不同的动力学特性.弯曲振动态(010)的吸收谱呈现出两波瓣的形状且中间具有较浅的极小值,其基态产物OD( ~X)在高能量区域会出现轻微的振动态反转现象.所有初始振动态得到的激发态产物OD(?)的振-转态分布都随能量的变化出现强烈的震荡,这是由于受到了激发态势能面上长寿命共振态的影响.反对称伸缩振动态(0,0,1)在高能量区域具有较大的产物分支比OD(?)/OD( ~X),表明绝热通道在某些情形下是主要的解离通道.
关键词:  光解,重水,振动激发态,锥形交叉,量子动力学
DOI:10.1063/1674-0068/28/cjcp1506138
分类号: