| Theoretical analysis of photoinduced H-atom elimination in thiophenol | |
| Venkatesan, T. S.1,2; Ramesh, S. G.1,3; Lan, Z.4; Domcke, W.1 | |
| 2012-05-07 | |
| 发表期刊 | JOURNAL OF CHEMICAL PHYSICS
 |
| 卷号 | 136期号:17 |
| 摘要 | The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative 1πσ* excited state with the bound 1ππ* excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the 1ππ*-1πσ* and 1πσ*-S0 conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S0, 1ππ*, 1πσ*) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the 1ππ* and 1πσ* states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the 2σ/2π electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (ν16a) and ring-distortion (ν16b) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor.; The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative (1)pi sigma* excited state with the bound (1)pi pi* excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the (1)pi pi*-(1)pi sigma* and (1)pi sigma*-S-0 conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S-0, (1)pi pi*, (1)pi sigma*) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the (1)pi pi* and (1)pi sigma* states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the (2)sigma/(2)pi electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (nu(16a)) and ring-distortion (nu(16b)) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4709608] |
| 文章类型 | Article |
| 学科领域 | 多相催化转化 |
| WOS标题词 | Science & Technology ; Physical Sciences |
| DOI | 10.1063/1.4709608 |
| 关键词[WOS] | PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY ; NEAR-ULTRAVIOLET PHOTOLYSIS ; INTRAMOLECULAR ORBITAL ALIGNMENT ; PHOTODISSOCIATION DYNAMICS ; CONICAL INTERSECTIONS ; UV PHOTOLYSIS ; (1)PI-SIGMA-ASTERISK STATES ; SUBSTITUTED PHENOLS ; EXCITED-STATE ; MODEL SYSTEMS |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS研究方向 | Physics |
| WOS类目 | Physics, Atomic, Molecular & Chemical |
| WOS记录号 | WOS:000303935700033 |
| 引用统计 | |
| 文献类型 | 期刊论文 |
| 条目标识符 | http://ir.qibebt.ac.cn/handle/337004/1260 |
| 专题 | 多相催化转化研究组 |
| 作者单位 | 1.Tech Univ Munich, Dept Chem, D-85747 Garching, Germany 2.Univ Texas Austin, Dept Chem & Biochem, Austin, TX 78712 USA 3.Indian Inst Sci, Dept Inorgan & Phys Chem, Bangalore 560012, Karnataka, India 4.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao 266101, Peoples R China |
| 推荐引用方式 GB/T 7714 | Venkatesan, T. S.,Ramesh, S. G.,Lan, Z.,et al. Theoretical analysis of photoinduced H-atom elimination in thiophenol[J]. JOURNAL OF CHEMICAL PHYSICS,2012,136(17). |
| APA | Venkatesan, T. S.,Ramesh, S. G.,Lan, Z.,&Domcke, W..(2012).Theoretical analysis of photoinduced H-atom elimination in thiophenol.JOURNAL OF CHEMICAL PHYSICS,136(17). |
| MLA | Venkatesan, T. S.,et al."Theoretical analysis of photoinduced H-atom elimination in thiophenol".JOURNAL OF CHEMICAL PHYSICS 136.17(2012). |
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