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Acta Phys. -Chim. Sin.  2012, Vol. 28 Issue (07): 1570-1578    DOI: 10.3866/PKU.WHXB201204173
THERMODYNAMICS, KINETICS, AND STRUCTURAL CHEMISTRY     
Dynamic Structures of 2-Thiopyrimidone and 2-Thiopyridone in B-Band Absorptions
GUO Xiao-Nan1, DU Rui1, ZHAO Yan-Ying1, PEI Ke-Mei1, WANG Hui-Gang1, ZHENG Xu-Ming1,2,3
1. Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China;
2. Key Laboratory of Advanced Textiles Materials and Manufacturing Technology of the Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China;
3. Engineering Research Center for Eco-dyeing and Finishing of Textiles of the Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China
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Abstract  

The dynamic structures of 2-thiopyrimidone (2TPM) and 2-thiopyridone (2TP) in B-band absorptions were studied using the resonance Raman spectroscopy combined with quantum chemical calculations. In gas phase, 2-thiopyrimidine (2MPM, the thiol form) was more stable than 2TPM (the thione form) by ~15.1 kJ·mol-1, whereas in water and acetonitrile 2TPM was more stable than 2MPM by 29.3 and 28.0 kJ·mol-1, respectively. The transition barrier for the ground state proton transfer tautomerization reaction between 2TPM and 2MPM was ~130 kJ·mol-1 in gas phase on the basis of the B3LYP/6-311++ G(d,p) level of theory calculations. The three absorption bands of 2-thiopyrimidone were respectively assigned as πH→πL*, πH→πL+1*, and πH-1→πL* transitions. The vibrational assignments were carried out for the B-band resonance Raman spectra of 2TPM in water and acetonitrile solvents on the basis of the measurements from the Fourier transform (FT)-Raman and Fourier transform-infrared (FT-IR) spectra of 2TPM in solid and/or in solution phases and B3LYP/6-311++G(d,p) computations. The dynamic structures of 2TPM and 2TP were obtained by analysis of the resonance Raman intensity pattern. The differences in the dynamic structures of 2TPM and 2TP reflected differences in the structures of their ππ*/πσ* conical intersection points, and therefore could be used to provide insight into the photoinduced hydrogen-atom detachment-attachment mechanism.

Key words： Thiol-thione phototautomeric reaction      Resonance Raman spectroscopy      Conical intersection      Excited-state structural dynamics      Vibrational spectrum      Density functional theory     
Received: 07 February 2012      Published: 17 April 2012
MSC2000:  O641  
Fund:  

The project was supported by the National Natural Science Foundation of China (21033002) and National Key Basic Research Program of China (973) (2007CB815203).
Corresponding Authors: ZHENG Xu-Ming     E-mail: zxm@zstu.edu.cn
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GUO Xiao-Nan
DU Rui
ZHAO Yan-Ying
PEI Ke-Mei
WANG Hui-Gang
ZHENG Xu-Ming
Cite this article:

GUO Xiao-Nan, DU Rui, ZHAO Yan-Ying, PEI Ke-Mei, WANG Hui-Gang, ZHENG Xu-Ming. Dynamic Structures of 2-Thiopyrimidone and 2-Thiopyridone in B-Band Absorptions. Acta Phys. -Chim. Sin., 2012, 28(07): 1570-1578.

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http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201204173     OR     http://www.whxb.pku.edu.cn/Y2012/V28/I07/1570

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