Citation: XU Zong-Ping, ZHAO Yan-Ying, WANG Hui-Gang, ZHENG Xu-Ming. Resonance Raman Spectroscopy and Density Functional Theory Investigations on the Excited State Structural Dynamics of N-Methylpyrrole-2-carboxaldehyde and Its Solvent Effect[J]. Acta Physico-Chimica Sinica, ;2012, 28(01): 65-72. doi: 10.3866/PKU.WHXB20122865 shu

Resonance Raman Spectroscopy and Density Functional Theory Investigations on the Excited State Structural Dynamics of N-Methylpyrrole-2-carboxaldehyde and Its Solvent Effect

1.
Key Laboratory of Advanced Textiles Materials and Manufacture Technology, and Engineering Research Center for Eco-dyeing and Finishing of Textiles, Ministry of Education, Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China

Received Date: 30 August 2011
Available Online: 7 November 2011
Fund Project: 国家重点基础研究发展规划(2007CB815203) (2007CB815203) 国家自然科学基金(21033002, 20803066) (21033002, 20803066)浙江省自然科学基金(Y4090161)资助项目 (Y4090161)

Resonance Raman spectra of N-Methylpyrrole-2-carboxaldehyde (NMPCA) were obtained and seven excitations covered the A- and B-band electronic absorptions. The electronic excitations and the Franck-Condon region structural dynamics of NMPCA were studied by resonance Raman spectroscopy and time-dependent density functional theory (TD-DFT) calculations. The A- and B-band electronic absorptions were assigned to π →π^* transitions on the basis of the TD-B3LYP/6-311 ++ G(d,p) level of theory. The resonance Raman spectra showed Raman intensity in the fundamentals, the overtones and the combination bands for about 11-13 vibrational modes (A-band excitation) or 7-11 vibrational modes (B-band excitation). These were predominately due to the C＝O stretch mode ν₇, the ring deformation+N₁－ C₆ stretch ν₁₇, the ring deformation mode ν₂₁ and the C₆－N₁－C₂/C₂－C₃－C₄ anti-symmetry stretch mode ν₁₄. This indicates that the Franck-Condon region S_π structural dynamics of NMPCA mainly occurs along the C＝O stretch, the ring deformation, and the N₁－C₆ stretch reaction coordinates. In a certain solvent and under different excitation wavelengths the relative intensity of the C＝O stretch mode ν₇ versus the C₆－N₁－C₂/C₂－C₃ －C₄ anti-symmetry stretch mode ν₁₄ shows an intense to weak to intense change as the excitation wavelengths decrease. This intensity variation directly reflects the S_n/S_π state-mixing or crossing of the potential energy surfaces in the Franck-Condon region. Solvents can efficiently tune the Franck- Condon region S_n/S_π state-mixing or crossing processes.
- N-Methylpyrrole-2-carboxaldehyde,
- Excited state structural dynamics,
- Resonance Raman spectrum,
- Solvent effect
1. [1]
  (1) Wagner, P. J. Acc. Chem. Res. 1971, 4, 168.
2. [2]
  (2) Gilbert, A.; Bag tt, J. Essentials of Molecular Photochemistry; CRC Press: Boca Raton, FL, 1991.
3. [3]
  (3) Horspool,W.; Armesto D. Organic Photochemistry-A Comprehensive Treatment; Ellis Horwood: New York, 1992.
4. [4]
  (4) Smolarek, J.; Zwarich, R.; odman, L. J. Mol. Spectrosc. 1972, 43, 416.
5. [5]
  (5) Abe, H.; Kamei, S.; Mikami, N.; Ito M. Chem. Phys. Lett. 1984, 109, 217.
6. [6]
  (6) Ohmori, N.; Suzuki, T.; Ito, M. J. Phys. Chem. 1988, 92, 1086.
7. [7]
  (7) Robin, M. B.; Kuebler, N. A. J. Am. Chem. Soc. 1975, 97, 4822.
8. [8]
  (8) Berger, M.; Steel, C. J. Am. Chem. Soc. 1975, 97, 4817.
9. [9]
  (9) Zhao, H. Q.; Cheung, Y. S.; Liao, C. L.; Liao, C. X.; Ng, C. Y.; Li,W. K. J. Chem. Phys. 1997, 107, 7230.
10. [10]
  (10) Anand, S.; Zamari, M. M.; Menkir, G.; Levis, R. J.; Schlegel, H. B. J. Phys. Chem. A 2004, 108, 3162.
11. [11]
  (11) Hirata, Y.; Lim, E. C. J. Chem. Phys. 1980, 72, 5505.
12. [12]
  (12) Hirata, Y.; Lim, E. C. Chem. Phys. Lett. 1980, 71, 167.
13. [13]
  (13) Koyanagi, M.; odman, L.; Chem. Phys. 1979, 39, 237.
14. [14]
  (14) Hayashi, H.; Nagakura, S. Mol. Phys. 1974, 27, 969.
15. [15]
  (15) Koyanagi, M.; Zwarich, R. J.; odman, L. J. Chem. Phys. 1972, 56, 3044.
16. [16]
  (16) Kiritani, M.; Yoshii, T.; Hirota, N.; Baba, M.; J. Phys. Chem. 1994, 98, 11265.
17. [17]
  (17) Villa, E.; Amirav, A.; Chen,W.; Lim, E. C. Chem. Phys. Lett. 1988, 147, 43.
18. [18]
  (18) Sneh, O.; Cheshnovsky, O. J. Phys. Chem. 1991, 95, 7154.
19. [19]
  (19) Fang,W. H.; Phillips, D. L. ChemPhysChem 2002, 3, 889.
20. [20]
  (20) Wang, Y.W.; He, H. Y.; Fang,W. H. J. Mol. Struct.- Theochem 2003, 634, 281.
21. [21]
  (21) Ding,W. J.; Fang,W. H. Progress in Chemistry 2007, 19, 1449. [丁万见, 方维海. 化学进展, 2007, 19, 1449.]
22. [22]
  (22) Srinivasan, R.; Feenstra, J. S.; Park, S. T.; Xu, S. J.; Zewail, A. H. Science 2005, 307, 558.
23. [23]
  (23) Feenstra, J. S.; Park, S. T.; Zewail, A. H. J. Chem. Phys. 2005, 123, 221104.
24. [24]
  (24) Park, S. T.; Feenstra, J. S.; Zewail, A. H. J. Chem. Phys. 2006, 124, 174707.
25. [25]
  (25) Ma, Y.; Pei, K.; Zheng, X.; Li H. Chem. Phys. Lett. 2007, 449, 107.
26. [26]
  (26) Li, S. P.;Wu, G. M.; Zheng, X. M. Chem. J. Chin. Univ. 2004, 25, 1495. [李少鹏, 吴光明, 郑旭明. 高等学校化学学报, 2004, 25, 1495.]
27. [27]
  (27) Myer, A. B.; Li, B.; Ci, X. J. Chem. Phys. 1988, 89, 1876.
28. [28]
  (28) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al . Gaussian 03, Revision B.02; Gaussian Inc.: Pittsburgh, PA, 2003.
29. [29]
  (29) Rauhut, G.; Pulay, P. J. Phys. Chem. 1995, 99, 3093.
30. [30]
  (30) Marian, C. M. J. Chem. Phys. 2005, 122, 104314.
31. [31]
  (31) Galica, G. E.; Johnson, B. R.; Kinsey, J. L.; Hale, M. O. J. Phys. Chem. 1991, 95, 7994.
32. [32]
  (32) Markel, F.; Myers, A. B. J. Chem. Phys. 1993, 98, 21.
33. [33]
  (33) Phillips, D. L.; Myers, A. B. J. Chem. Phys. 1991, 95, 226.
34. [34]
  (34) Kwok,W. M.; Phillips, D. L. J. Chem. Phys. 1996, 104, 9816.
35. [35]
  (35) Zheng, X.; Phillips, D. L. Chem. Phys. Lett. 1998, 286, 79.
36. [36]
  (36) Santoro, F.; Barone, V.; Gustavsson, T.; Improta, R. J. Am. Chem. Soc. 2006, 128, 16312.
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