Citation: LIU Chong, DU Rui, ZHAO Yan-Ying, WANG Hui-Gang, ZHENG Xu-Ming. Resonance Raman Spectroscopy of the Excited State Structural Dynamics of 6-N,N-Dimethyladenine[J]. Acta Physico-Chimica Sinica, ;2011, 27(01): 17-24. doi: 10.3866/PKU.WHXB20110132 shu

Resonance Raman Spectroscopy of the Excited State Structural Dynamics of 6-N,N-Dimethyladenine

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 Science and Technology University, Hangzhou 310018, P. R. China

Received Date: 13 August 2010
Available Online: 13 December 2010
Fund Project: 国家重点基础研究发展规划(973) (2007CB815203) (973) (2007CB815203) 国家自然科学基金(21033002, 20573097) (21033002, 20573097)浙江省自然科学基金(R405465)资助项目 (R405465)

The A- and B-band electronic excitations and the excited state structural dynamics of 6-N,N-dimethyladenine (DMA) were studied by resonance Raman spectroscopy and density functional theory calculations. The π_H→π_L^* transition is the main part of the A-band absorption and its calculated oscillator strength occupies 79% of the A-band absorption. n→Ryd and π_H→Ryd transitions where Ryd denotes the diffuse Rydberg orbital play important roles in the B-band electronic transitions and their calculated oscillator strengths occupy about 62% of the B-band absorption. The oscillator strength for the π_H→π_L^* transition, which dominates the A-band electronic transition only occupies about 33% of the B-band absorption. The foundamental vibrations of the purine ring deformation stretch plus the C8H/N9H bend mode ν₂₃ and the 5 member ring deformation stretch plus the C8H bend mode ν₁₃, and their overtones and combination bands occupy most of the A-band resonance Raman intensities. Therefore, the ¹π_Hπ_L^* excited state structural dynamics of DMA is mainly along the ν₂₃ and ν₁₃ reaction coordinates. The majority of the B-band resonance Raman intensities are dominated by the fundamental vibrations of ν₁₀, ν₂₉, ν₂₁, ν₂₆, ν₄₀, and their overtones and combination bands. This suggests the B-band excited state structural dynamics of DMA is mostly along the purine ring deformation, the C6N10 stretch, the N9H/C8H/C2H bend and the N(CH₃)₂ antisymmetric stretch. The appearance of ν₂₆ and ν₁₂ in the A-band resonance Raman spectrum is correlated to the Franck-Condon region ¹nπ^*/¹ππ^* conical intersection. The activation of ν₂₁ in the B-band resonance Raman spectrum is correlated to the Franck-Condon region ¹ππ^*/¹πσ_N9H^* conical intersection.
- 6-N,N-dimethyladenine,
- Excited state structural dynamics,
- Resonance Raman spectrum,
- Electronic transition
1. [1]
  
  1 Crespo-Hemández, C. E.; Cohen, B.; Hare, P. M.; Kohler, B. Chem. Rev., 2004, 104: 1977
2. [2]
  2 Sobolewski, A. L.; Domcke,W.; Dedonder-Lardeux, C.; Jouvet, C. Phys. Chem. Chem. Phys., 2002, 4: 1093
3. [3]
  3 Perun, S.; Sobolewski, A. L.; Domcke,W. J. Am. Chem. Soc., 2005, 127: 6257
4. [4]
  4 Perun, S.; Sobolewski, A. L.; Domcke,W. Chem. Phys., 2005, 313: 107
5. [5]
  5 Kang, H.; Jung, B.; Kim, S. K. J. Chem. Phys., 2003, 118: 6717
6. [6]
  6 Canuel, C.; Mons, M.; Piuzzi, F.; Tardivel, B.; Dimicoli, I.; Elhanine, M. J. Chem. Phys., 2005, 122: 074306
7. [7]
  7 Samoylova, E.; Lippert, H.; Ullrich, S.; Hertel, I. V.; Radloff,W.; Schultz, T. J. Am. Chem. Soc., 2005, 127: 1782
8. [8]
  8 Wells, K. L.; Roberts, G. M.; Stavros, V. G. Chem. Phys. Lett., 2007, 446: 20
9. [9]
  9 Wells, K. L.; Hadden, D. J.; Nix, M. G. D.; Stavros, V. G. J. Phys. Chem. Lett., 2010, 1: 993
10. [10]
  10 Zierhut, M.; Roth,W.; Fischer, I. Phys. Chem. Chem. Phys., 2004, 6: 5178
11. [11]
  11 Satzger, H.; Townsend, D.; Zgierski, M. Z.; Patchovskii, S.; Ullrich, S.; Stolow, A. Proc. Natl. Acad. Sci. U. S. A., 2006, 103: 10196
12. [12]
  12 Nix, M. G. D.; Devine, A. L.; Cronin, B.; Ashfold, M. N. R. J. Chem. Phys., 2007, 126: 124312
13. [13]
  13 Ullrich, S.; Schultz, T.; Zgierski, M. Z.; Stolow, A. Phys. Chem. Chem. Phys., 2004, 6: 2796
14. [14]
  14 Ullrich, S.; Schultz, T.; Zgierski, M. Z.; Stolow, A. J. Am. Chem. Soc., 2004, 126: 2262
15. [15]
  15 Ritze, H. H.; Lippert, H.; Samoylova, E.; Smith, V. R.; Hertel, I. V.; Radloff,W.; Schultz, T. J. Chem. Phys., 2005, 122: 224320
16. [16]
  16 Longworth, J.W.; Rahn, R. O.; Shulman, R. G. J. Chem. Phys., 1966, 45: 2930
17. [17]
  17 Wilson, R.W.; Callis, P. R. Photochem. Photobiol., 1974, 20: 345
18. [18]
  18 Eastman, J.W. Ber. Bunsen-Ges. Phys. Chem., 1969, 75: 407
19. [19]
  19 Parusel, A. B. J.; Rettig,W.; Rotkiewicz, K. J. Phys. Chem. A, 2002, 106: 2293
20. [20]
  20 Schwalb, N. K.; Temps, F. Phys. Chem. Chem. Phys., 2006, 8: 5229
21. [21]
  21 Li, S. P.;Wu, G. M.; Zheng, X. M. Chem. J. Chin. Univ., 2004, 25: 1495
22. [22]
  [李少鹏, 吴光明, 郑旭明. 高等学校化学学报, 2004, 25: 1495]
23. [23]
  22 Myer, A. B.; Li, B.; Ci, X. J. Chem. Phys., 1988, 89: 1876
24. [24]
  23 Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision B.02. Pittsburgh, PA: Gaussian Inc., 2003
25. [25]
  24 Sadlej-Sosnowska, N.; Kry wski, T. M. Chem. Phys. Lett., 2009, 476: 191
26. [26]
  25 Rauhut, G.; Pulay, P. J. Phys. Chem., 1995, 99: 3091
27. [27]
  26 Marian, C. M. J. Chem. Phys., 2005, 122: 104314
28. [28]
  27 Foresman, J. B.; Keith, T. A.;Wiberg, K. B.; Snoonian, J.; Frisch, M. J. J. Phys. Chem., 1996, 100: 16098
29. [29]
  28 Wu, X. F.; Zheng X.;Wang, H. G.; Zhao, Y.Y.; Guan X. G.; Phillips, D. L.; Chen, X. B.; Fang,W. H. J. Chem. Phys., 2010, 133: 134507
30. [30]
  29 Conti, I.; Garavelli, M.; Orlandi, G. J. Am. Chem. Soc., 2009, 131: 16118
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沈阳化工大学材料科学与工程学院沈阳 110142