Theory of Excited State Decays and Optical Spectra: Application to Polyatomic Molecules
文献类型：期刊论文
| 作者 | Niu, Yingli1; Peng, Qian1; Deng, Chunmei; Gao, Xing2; Shuai, Zhigang1,2 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2010-08-05 |
| 卷号 | 114期号:30页码:7817-7831 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp101568f |
| 英文摘要 | General formalism of absorption and emission spectra, and of radiative and nonradiative decay rates are derived using a thermal vibration correlation function formalism for the transition between two adiabatic electronic states in polyatomic molecules. Displacements, distortions, and Duschinsky rotation of potential energy surfaces are included within the framework of a multidimensional harmonic oscillator model. The Herzberg-Teller (HT) effect is also taken into account. This formalism gives a reliable description of the Q(x) spectral band of free-base porphyrin with weakly electric dipole-allowed transitions. For the strongly dipole-allowed transitions, e.g., S-1 -> S-0 and S-0 -> S-1 of linear polyacenes, anthracene, tetracene, and pentacene, the HT effect is found to enhance the radiative decay rates by -> 10% compared to those without the HT effect. For nonradiative transition processes, a general formalism is presented to extend the application scope of the internal conversion theory by going beyond the promoting-mode approximation. Numerical calculations for the nonradiative S-1 -> S-0 decay rate of azulene well explain the origin of the violation of Kasha's rule. When coupled with first-principles density functional theory (DFT) calculations, the present approach appears to be an effective tool to obtain a quantitative description and detailed understanding of spectra and photophysical processes in polyatomic molecules. |
| 语种 | 英语 |
| WOS记录号 | WOS:000280360800001 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71085]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Shuai, Zhigang |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, BNLMS, Key Lab Organ Solids, Beijing 100190, Peoples R China 2.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China |
| 推荐引用方式 GB/T 7714 | Niu, Yingli,Peng, Qian,Deng, Chunmei,et al. Theory of Excited State Decays and Optical Spectra: Application to Polyatomic Molecules[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2010,114(30):7817-7831. |
| APA | Niu, Yingli,Peng, Qian,Deng, Chunmei,Gao, Xing,&Shuai, Zhigang.(2010).Theory of Excited State Decays and Optical Spectra: Application to Polyatomic Molecules.JOURNAL OF PHYSICAL CHEMISTRY A,114(30),7817-7831. |
| MLA | Niu, Yingli,et al."Theory of Excited State Decays and Optical Spectra: Application to Polyatomic Molecules".JOURNAL OF PHYSICAL CHEMISTRY A 114.30(2010):7817-7831. |
入库方式： OAI收割
来源：化学研究所
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