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化学进展 2012, Vol. 24 Issue (06): 928-949 前一篇   后一篇

• 量子化学专辑 •

无辐射跃迁理论进展

牛英利1, 林至闓2, 杨玲3, 于建国4, 何荣幸5, 庞然6, 朱超原*2, 林倫年7, 林聖賢2   

  1. 1. 中国科学院化学研究所有机固体重点实验室 北京 100190;
    2. 西北大学现代物理研究所 西安 710069;
    3. 哈尔滨工业大学基础与交叉科学研究院理论与模拟化学研究所 哈尔滨 150080;
    4. 北京师范大学化学学院 北京 10087;
    5. 西南大学化学化工学院 重庆 400715;
    6. 厦门大学化学化工学院固体表面物理化学国家重点实验室 厦门 361005;
    7. 东北大学理学院化学系 仙台 日本 980
  • 收稿日期:2012-02-01 修回日期:2012-04-01 出版日期:2012-06-24 发布日期:2012-05-11
  • 通讯作者: 朱超原 E-mail:cyzhu@mail.nctu.edu.tw
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Recent Developments in Radiationless Transitions

Niu Yingli1, Lin Chinkai2, Yang Ling3, Yu Jianguo4, He Rongxing5, Pang Ran6, Zhu Chaoyuan2, Hayashi Michitoshi7, Lin Sheng Hsien2   

  1. 1. Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;
    2. Institute of Modern Physics, Northwest University, Xian 710069, China;
    3. Institute of Theoretical and Simulation Chemistry, Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin 150080 China;
    4. Department of Chemistry, Beijing Normal University, Beijing 10087;
    5. College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China;
    6. State Key Laboratory of Physical Chemistry of Solid Surfaces, and College of Chemistry and Chemical Engineering and Xiamen University, Xiamen, 361005, Fujian, China;
    7. Department of Chemistry, Faculty of Science, Tohoku University, Sendai 980, Japan
  • Received:2012-02-01 Revised:2012-04-01 Online:2012-06-24 Published:2012-05-11
在本文中,我们将介绍运用第一性原理计算包含非谐效应或势能面锥形交叉情况下内转换速率的最新工作。我们同时计算了包含非谐效应的分子吸收和发射光谱,以检验量子化学方法计算得到势能面的准确性。势能面的锥形交叉对内转换过程的影响是学界广泛关注的焦点。本文将介绍如何在内转换速率计算的过程中考虑势能面锥形交叉的影响,并将之运用于吡嗪分子。本文运用绝热近似理论处理了另外一个重要的无辐射过程,分子的振动驰豫过程,并将这个理论应用于水二聚体和苯胺的振动弛豫速率的计算。
关键词： 无辐射跃迁, 内转换, 振动弛豫, 双井势, 非谐效应
In this paper, we will introduce recent works on the mathematical treatments and the first-principle calculations concerning the internal conversion rates for the cases with anharmonic potentials, and conical intersecting potentials. The simulations of absorption and emission spectra with anharmonic effects are also presented to check the validity of the potential energy surfaces obtained from the quantum chemical calculations. The effect of conical intersection on internal conversion has attracted considerable attention. In this paper a different approach will be proposed and applied to pyrazine. Another important non-radiative process, molecular vibrational relaxation, is also treated by applying the adiabatic approximation to the ab initio anharmonic potential energy surfaces in this paper. The vibrational relaxation rates in water dimer and aniline are chosen to demonstrate the calculation.
Key words: radiationless transition, internal conversion, vibrational relaxation, double well potential, anharmonic effect

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摘要

无辐射跃迁理论进展