Home

Citation: ZHU Yue, PU Min, HE Jing, EVANS David G.. Photoisomerization Mechanism of the Trans-cis Azobenzene Sulphonate Derivatives[J]. Acta Physico-Chimica Sinica, ;2009, 25(11): 2296-2304. doi: 10.3866/PKU.WHXB20091009 shu

Photoisomerization Mechanism of the Trans-cis Azobenzene Sulphonate Derivatives

1.
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Received Date: 21 April 2009
Available Online: 24 August 2009

Photoisomerization pathways for 3,3'-azobenzene sulfonate (3,3'-AbS) in the S0 and T1 states were studied by using density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In the S0 state, there are two isomerization pathways: the inversion of one NNC angle combined with the rotation around the NC bond and the rotation of the CNNC dihedral angle. The energy barriers of the two pathways are 94.2 and 124.3 kJ·mol-1, respectively. It is worthy to notice that there exist second-order transition states on the combination pathways of inversion and rotation. In the T1 state, only the rotation pathway exists and its energy barrier is 21.1 kJ·mol-1. To investigate the photoisomerization pathway, the potential energy profiles of the vertical excitation for the excited states (T1, S1, T2, and S2) were calculated by time dependent density functional theory (TD-DFT) at the B3LYP/6-311++G(d,p) level along the two pathways. A photoexcitation at 330 nm results in the reactant molecule populating the S2 state and then under ing a rapid relaxation to the minimum of the S1 state. Two possible isomerization pathways exist through the rotation pathway as follows: (1) the isomerization can easily occur through the S0/S1 conical intersection (CI) and descend to the S0 state; (2) a relaxation to the T1 state from the S1 state may occur and the reaction can take place via the S0-T1-S0 path. Calculation results show that the primary isomerization pathways for 3,3'-AbS are a combination pathway of inversion and rotation in the S0 state and the rotation pathway when it is excited.
- Density fuctional theory,
- 3,3’-azobenzene sulphonate,
- Photoisomerization mechanism,
- Excited state,
- Potential energy profile
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
3. [3]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
4. [4]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
5. [5]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
6. [6]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
7. [7]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
8. [8]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
9. [9]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
10. [10]
  Qingjun PAN , Zhongliang GONG , Yuwu ZHONG . Advances in modulation of the excited states of photofunctional iron complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 45-58. doi: 10.11862/CJIC.20240365
11. [11]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
12. [12]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
13. [13]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
14. [14]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
15. [15]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
16. [16]
  Yihao Zhao , Jitian Rao , Jie Han . Synthesis and Photochromic Properties of 3,3-Diphenyl-3H-Naphthopyran: Design and Teaching Practice of a Comprehensive Organic Experiment. University Chemistry, 2024, 39(10): 149-155. doi: 10.3866/PKU.DXHX202402050
17. [17]
  Hui Li , Jia Nie , Zhongyuan Lü , Hujun Qian , Youliang Zhu , Fuquan Bai , Zexing Qu , Ronglin Zhong . Developing a Lecture Mode for Theoretical and Computational Chemistry Curriculum under the “Modernization of Chinese Education” Initiative. University Chemistry, 2025, 40(3): 1-9. doi: 10.3866/PKU.DXHX202402007
18. [18]
  Yuena Yu , Fang Fang . Microwave-Assisted Synthesis of Safinamide Methanesulfonate. University Chemistry, 2024, 39(11): 210-216. doi: 10.3866/PKU.DXHX202401076
19. [19]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125
20. [20]
  Lianghong Ye , Junqing Ni , Zhongyi Yan , Zhanming Zhang , Can Zhu , Mo Sun . Chemical Fuel-Driven Non-Equilibrium Color Change. University Chemistry, 2025, 40(3): 349-354. doi: 10.12461/PKU.DXHX202406109

Get Citation

PDF

XML

Metrics

PDF Downloads(1668)
Abstract views(4390)
HTML views(39)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888

DownLoad: Full-Size Img PowerPoint

Return