Citation: QIN Chen, TZENG Sheng-Yuan, ZHANG Bing, TZENG Wen-Bih. Rotamers of m-Methylanisole Studied by Mass-Analyzed Threshold Ionization Spectroscopy[J]. Acta Physico-Chimica Sinica, ;2014, 30(8): 1416-1425. doi: 10.3866/PKU.WHXB201405232 shu

Rotamers of m-Methylanisole Studied by Mass-Analyzed Threshold Ionization Spectroscopy

1.
1. Laboratory for Mass Spectrometric and Spectroscopic Studies of Biomolecules, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617;
2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071;
3. Key Laboratory of Novel Luminescent Materials and Nanostructures, College of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054

Received Date: 23 April 2014
Available Online: 23 May 2014

The S₁←S₀ electronic transition and threshold ionization of the cis and trans rotamers of m-methylanisole were investigated by using one- color resonant two- photon ionization and mass- analyzed threshold ionization techniques. The first electronic excitation energies (E₁) of the cis and trans rotamers were determined to be (36049±2) and (36117±2) cm^-1, while the adiabatic ionization energies (I_p) were (64859 ± 5) and (65110 ± 5) cm^-1, respectively. The results of ab initio and density functional theory calculations provide a satisfactory interpretation for our experimental findings concerning the difference in the transitional energies of the cis and trans rotamers and assist in assigning the vibronic and cation spectra obtained in the present study. The observed active vibrations of both rotamers in the S₁ and D₀ states primarily consist of methyl torsion, in- plane ring deformation, and substituent- sensitive bending modes. Both experimental and theoretical results show that, for both cis and trans isomers, the geometry of the cation in the D0 state is somewhat different from that of the neutral species in the S₁ state. In addition, the strengths of both the through- space substituent- substituent and substituent- ring interactions were found to follow the order: S₀<S₁<D₀.
- m-Methylanisole,
- Rotamer,
- Vibronic spectrum,
- Threshold ionization,
- Cation spectrum
1. [1]
  
  (1) Dian, B. C.; Longarte, A.;Winter, P. R.; Zwier, T. S. J. Chem. Phys. 2004, 120, 133. doi: 10.1063/1.1626540
2. [2]
  (2) Pan, C. P.; Barkley, M. D. Biophys. J. 2004, 86, 3828. doi: 10.1529/biophysj.103.038901
3. [3]
  (3) Oikawa, A.; Abe, H.; Mikami, N.; Ito, M. Chem. Phys. Lett. 1985, 116, 50. doi: 10.1016/0009-2614(85)80123-8
4. [4]
  (4) McMurry, J. Organic Chemistry, 7th ed.; Brooke/Cole Publishing Company: Belmont, California, 2007.
5. [5]
  (5) Breen, P. J.; Bernstein, E. R.; Secor, H. V.; Seeman, J. I. J. Am. Chem. Soc. 1989, 111, 1958. doi: 10.1021/ja00188a002
6. [6]
  (6) Ichimura, T.; Suzuki, T. J. Photochem. Photobiol. C: Photochem. Rev. 2000, 1, 79. doi: 10.1016/S1389-5567(00)00006-X
7. [7]
  (7) Kojima, H.; Miyake, K.; Sakeda, K.; Suzuki, T.; Ichimura, T.; Tanaka, N.; Negishi, D.; Takayanagi, M.; Hanazaki, I. J. Mol. Struct. 2003, 655, 185. doi: 10.1016/S0022-2860(03)00258-8
8. [8]
  (8) Alvarez-Valtierra, L.; Yi, J. T.; Pratt, D.W. J. Phys. Chem. B 2006, 110, 19914. doi: 10.1021/jp062050h
9. [9]
  (9) Kinoshita, S.; Kojima, H.; Suzuki, T.; Ichimura, T.; Yoshida, K.; Sakai, M.; Fujii, M. Phys. Chem. Chem. Phys. 2001, 3, 4889. doi: 10.1039/b105719g
10. [10]
  (10) Pradhan, M.; Li, C.; Lin, J. L.; Tzeng,W. B. Chem. Phys. Lett. 2005, 407, 100. doi: 10.1016/j.cplett.2005.03.068
11. [11]
  (11) Lu, K. T.; Eiden, G. C.;Weisshaar, J. C. J. Phys. Chem. 1992, 96, 9742. doi: 10.1021/j100203a032
12. [12]
  (12) Shiung, K. S.; Yu, D.; Huang, H. C.; Tzeng,W. B. J. Mol. Spectrosc. 2012, 274, 43. doi: 10.1016/j.jms.2012.04.004
13. [13]
  (13) Ullrich, S.; Geppert,W. D.; Dessent, C. E. H.; Müller-Dethlefs, K. J. Phys. Chem. A 2000, 104, 11864.
14. [14]
  (14) Yang, S. C.; Huang, S.W.; Tzeng,W. B. J. Phys. Chem. A 2010, 114, 11144. doi: 10.1021/jp1026652
15. [15]
  (15) Lin, J. L.; Huang, C. J.; Lin, C. H.; Tzeng,W. B. J. Mol. Spectrosc. 2007, 244, 1. doi: 10.1016/j.jms.2007.05.001
16. [16]
  (16) Zhang, S.; Tang, B. F.;Wang, Y. M.; Zhang, B. Chem. Phys. Lett. 2004, 397, 495. doi: 10.1016/j.cplett.2004.09.025
17. [17]
  (17) Held, A.; Selzle, H. L.; Schlag, E.W. J. Phys. Chem. A 1998, 102, 9625.
18. [18]
  (18) Lin, J. L.; Lin, K. C.; Tzeng,W. B. J. Phys. Chem. A 2002, 106, 6462. doi: 10.1021/jp0204713
19. [19]
  (19) Okuyama, K.; Mikami, N.; Ito, M. Laser Chem. 1987, 7, 197. doi: 10.1155/LC.7.197
20. [20]
  (20) Huang, J.; Huang, K.; Liu, S.; Luo, Q.; Tzeng,W. B. J. Photochem. Photobiol. A: Chem. 2007, 188, 252. doi: 10.1016/j.jphotochem.2006.12.016
21. [21]
  (21) Huang, J.; Lin, J. L.; Tzeng,W. B. Spectrochim. Acta A 2007, 67, 989. doi: 10.1016/j.saa.2006.09.018
22. [22]
  (22) Tzeng,W. B.; Lin, J. L. J. Phys. Chem. A 1999, 103, 8612.
23. [23]
  (23) Sinclair,W. E.; Pratt, D.W. J. Chem. Phys. 1996, 105, 7942. doi: 10.1063/1.472710
24. [24]
  (24) Chupka,W. A. J. Chem. Phys. 1993, 98, 4520. doi: 10.1063/1.465011
25. [25]
  (25) Schlag, E.W. ZEKE Spectroscopy; Cambridge University Press: Cambridge, 1998; pp 40-41.
26. [26]
  (26) Zhang, B.; Li, C.; Su, H.; Lin, J. L.; Tzeng,W. B. Chem. Phys. Lett. 2004, 390, 65. doi: 10.1016/j.cplett.2004.04.013
27. [27]
  (27) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.02; Gaussian Inc.:Wallingford, CT, 2009.
28. [28]
  (28) Varsanyi, G. Assignments of Vibrational Spectra of Seven Hundred Benzene Derivatives;Wiley: New York, 1974; pp 185, 201.
29. [29]
  (29) Varsanyi G.; Szoke, S. Vibrational Spectra of Benzene Derivatives; Academic Press: New York, London, 1969.
30. [30]
  (30) Wilson, E. B. Phys. Rev. 1934, 45, 706. doi: 10.1103/PhysRev.45.706
31. [31]
  (31) Huang, H. C.; Shiung, K. S.; Jin, B. Y.; Tzeng,W. B. Chem. Phys. 2013, 425, 114. doi: 10.1016/j.chemphys.2013.08.013
32. [32]
  (32) Lin, J. L.; Li, Y. C.; Tzeng,W. B. Chem. Phys. 2007, 334, 189. doi: 10.1016/j.chemphys.2007.03.002
33. [33]
  (33) Yosida, K.; Suzuki, K.; Ishiuchi, S.; Sakai, M.; Fujii, M.; Dessent, C. E. H.; Müller-Dethlefs, K. Phys. Chem. Chem. Phys. 2002, 4, 2534. doi: 10.1039/b201107g
34. [34]
  (34) Shinozaki, M.; Sakai, M.; Yamaguchi, S.; Fujioka, T.; Fujii, M. Phys. Chem. Chem. Phys. 2003, 5, 5044. doi: 10.1039/b309461h
35. [35]
  (35) Xie, Y.; Su, H.; Tzeng,W. B. Chem. Phys. Lett. 2004, 394, 182. doi: 10.1016/j.cplett.2004.07.005
36. [36]
  (36) Xu, Y.; Tzeng, S. Y.; Tzeng,W. B. Spectrochim. Acta A 2013, 102, 365. doi: 10.1016/j.saa.2012.10.020
37. [37]
  (37) Tsai, C. Y.; Tzeng,W. B. J. Photochem. Photobiol. A 2013, 270, 53. doi: 10.1016/j.jphotochem.2013.07.014
1. [1]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
2. [2]
  Wenliang Wang , Weina Wang , Lixia Feng , Nan Wei , Sufan Wang , Tian Sheng , Tao Zhou . Proof and Interpretation of Severe Spectroscopic Selection Rules. University Chemistry, 2025, 40(3): 415-424. doi: 10.12461/PKU.DXHX202408063
3. [3]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
4. [4]
  Xiaolei Jiang , Fangdong Hu . Exploring the Mirror World in Organic Chemistry: the Teaching Design of “Enantiomers” from the Perspective of Curriculum and Ideological Education. University Chemistry, 2024, 39(10): 174-181. doi: 10.3866/PKU.DXHX202402052
5. [5]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, 2025, 40(3): 76-82. doi: 10.12461/PKU.DXHX202404119
6. [6]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
7. [7]
  Jingyi Chen , Fu Liu , Tiejun Zhu , Kui Cheng . Practice of Integrating Ideological and Political Education into Raman Spectroscopy Analysis Experiment Course. University Chemistry, 2024, 39(2): 140-146. doi: 10.3866/PKU.DXHX202310111
8. [8]
  Chun-Lin Sun , Yaole Jiang , Yu Chen , Rongjing Guo , Yongwen Shen , Xinping Hui , Baoxin Zhang , Xiaobo Pan . Construction, Performance Testing, and Practical Applications of a Home-Made Open Fluorescence Spectrometer. University Chemistry, 2024, 39(5): 287-295. doi: 10.3866/PKU.DXHX202311096
9. [9]
  Tianlong Zhang , Jiajun Zhou , Hongsheng Tang , Xiaohui Ning , Yan Li , Hua Li . Virtual Simulation Experiment for Laser-Induced Breakdown Spectroscopy (LIBS) Analysis. University Chemistry, 2024, 39(6): 295-302. doi: 10.3866/PKU.DXHX202312049
10. [10]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
11. [11]
  Zhaoyue Lü , Zhehao Chen , Yi Ni , Duanbin Luo , Xianfeng Hong . Multi-Level Teaching Design and Practice Exploration of Raman Spectroscopy Experiment. University Chemistry, 2024, 39(11): 304-312. doi: 10.12461/PKU.DXHX202402047
12. [12]
  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
13. [13]
  Mengyao Shi , Kangle Su , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Potassium Content in Tobacco Stem Ash by Flame Atomic Absorption Spectroscopy. University Chemistry, 2024, 39(10): 255-260. doi: 10.12461/PKU.DXHX202404105
14. [14]
  Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C₃N₄/Ti₃C₂T_x Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477
15. [15]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075
16. [16]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
17. [17]
  Yi Li , Zhaoxiang Cao , Peng Liu , Xia Wu , Dongju Zhang . Revealing the Coloration and Color Change Mechanisms of the Eriochrome Black T Indicator through Computational Chemistry and UV-Visible Absorption Spectroscopy. University Chemistry, 2025, 40(3): 132-139. doi: 10.12461/PKU.DXHX202405154
18. [18]
  Jiahui YU , Jixian DONG , Yutong ZHAO , Fuping ZHAO , Bo GE , Xipeng PU , Dafeng ZHANG . The morphology control and full-spectrum photodegradation tetracycline performance of microwave-hydrothermal synthesized BiVO₄:Yb³⁺,Er³⁺ photocatalyst. Journal of Fuel Chemistry and Technology, 2025, 53(3): 348-359. doi: 10.1016/S1872-5813(24)60514-1
19. [19]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
20. [20]
  Supin Zhao , Jing Xie . Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 178-185. doi: 10.12461/PKU.DXHX202406024

Get Citation

PDF

XML

Metrics

PDF Downloads(488)
Abstract views(558)
HTML views(3)

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