6-N,N-二甲基腺嘌呤激发态结构动力学的共振拉曼光谱

doi:10.3866/PKU.WHXB20110132

Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (01): 17-24.doi: 10.3866/PKU.WHXB20110132

• THERMODYNAMICS, KINETICS, AND STRUCTURAL CHEMISTRY • Previous Articles Next Articles

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

LIU Chong, DU Rui, ZHAO Yan-Ying, WANG Hui-Gang, ZHENG Xu-Ming

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:2010-08-13 Revised:2010-10-13 Published:2010-12-31
Contact: ZHENG Xu-Ming E-mail:zxm@zstu.edu.cn
Supported by:
The project was supported by the National Key Basic Research Program of China (973) (2007CB815203), National Natural Science Foundation of China (21033002, 20573097), and Natural Science Foundation of Zhejiang Province, China (R405465).

Abstract

Abstract:

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.

Key words: 6-N,N-dimethyladenine, Excited state structural dynamics, Resonance Raman spectrum, Electronic transition

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 Phys. -Chim. Sin. 2011, 27(01), 17-24. doi: 10.3866/PKU.WHXB20110132

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

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