引用本文:
【打印本页】   【HTML】   【下载PDF全文】   View/Add Comment  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 84次   下载 37 本文二维码信息
码上扫一扫!
分享到: 微信 更多
A Quantum Wavepacket Study of State-to-State Photodissociation Dynamics of HOBr/DOBr
Liang Zhang, Bin Jiang*
Hefei National Laboratory for Physical Science at the Microscale, Department of Chemical Physics, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei 230026, China
Abstract:
Photodissociation of HOBr is an important step in the reaction network of the depletion of ozone in stratosphere. Here, we report the first three-dimensional potential energy surfaces for the lowest three singlet states for HOBr, based on high level multi reference configuration interaction calculations. Quantum dynamics calculations are performed with a real wavepacket method, yielding not only absorption spectra but also internal state and angular distributions of the photodissociation fragments. Our results agree quantitatively with the measured total absorption cross sections of HOBr in the ultraviolet region and reproduce well the observed vibrationally cold and rotationally hot OH/OD fragments via photodissociation of HOBr/DOBr at 266 nm. In addition, we predict that the recoil anisotropy parameters for OH/OD are close to the limiting value of a parallel transition, suggesting a rapid dissociation process at 266 nm following an in-plane transition from the ground state (11A') to the 21A'state. This is consistent with the experimental conclusion derived from the measured rotational alignment. However, spin and electronic angular momenta need to be taken into account in the future to achieve a more quantitative agreement with experiment. Our work is expected to motivate further experimental investigations for this benchmark system.
Key words:  Potential energy surface, Photodissociation dynamics, Wavepacket
FundProject:
附件
HOBr/DOBr态到态光解动力学的量子波包研究
张 良, 蒋 彬*
中国科学技术大学化学物理系,合肥微尺度物质科学国家研究中心,安徽省高等学校表面与界面化学与能源催化重点实验室,合肥 230026
摘要:
本文基于高水平的多参考组态相互作用计算,报导了HOBr的最低三个单重态的三维势能面. 并且对该分子的光解离过程用实波包传播的方法进行了量子动力学研究,不仅计算结果得到了吸收光谱,而且还产生了光解产物的内态和角度分布. 结果与在紫外区域测得的HOBr的总吸收截面定量吻合,并很好的重现了实验上在266 nm处观察到的振动冷和转动热的光解OH/OD产物. 此外,预测了OH/OD的反冲各向异性参数接近平行跃迁的极限值,表明在266 nm处从基态(11A')到21A'态的面内跃迁是一个快速的解离过程. 这与实验上从测量转动取向得出的结论一致. 然而,想要实现与实验上的定量一致,还需要考虑自旋和电子角动量的影响.
关键词:  势能面,光解动力学,波包
DOI:10.1063/1674-0068/cjcp1911214
分类号: