间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱

引用本文: 秦晨, 曾圣渊, 张冰, 曾文碧. 间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱[J]. 物理化学学报, 2014, 30(8): 1416-1425. doi: 10.3866/PKU.WHXB201405232 shu

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

间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱

摘要:

间甲基苯甲醚分子有顺式和反式两个转动异构体. 利用单光共振双光子电离技术和质量分辨阈值电离技术，研究了间甲基苯甲醚分子顺反异构体的基态到第一电子激发态（S₁←S₀）的跃迁和阈值电离. 得到顺式、反式间甲基苯甲醚分子S₁态的激发能（E₁）分别为（36049±2）和（36117±2）cm^-1，绝热电离能（I_p）分别为（64859±5）和（65110±5）cm^-1. 结合从头算法和密度泛函理论的量子化学计算，解释了顺式、反式间甲基苯甲醚分子E₁和I_p存在差异的原因，并且对S₁态和离子基态D0态出现的谱峰进行了标识. 间甲基苯甲醚分子顺反异构体在S₁态和D₀态的活性振动主要是甲基转动、面内环的运动和与取代基相关的弯曲振动. 间甲基苯甲醚分子的S₁态振动光谱、D₀态离子光谱以及理论计算均表明这两个转动异构体在D₀态的几何构型与S₁态的中性几何构型相比有较大改变，取代基与取代基、取代基与苯环间的相互作用强度高低次序为：S₀<S₁<D₀.

关键词:

English

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: 18 July 2014

Abstract:

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.

Key words:

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
  (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(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(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.(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(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(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(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(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(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(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(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(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.(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(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(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(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.(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(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(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(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(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.(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(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(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.(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(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.(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.(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.(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(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(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(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(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(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(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(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
  (37) Tsai, C. Y.; Tzeng,W. B. J. Photochem. Photobiol. A 2013, 270, 53. doi: 10.1016/j.jphotochem.2013.07.014

扫一扫看文章

计量

PDF下载量: 488
文章访问数: 648
HTML全文浏览量: 4

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

间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs