2-硫代嘧啶酮和2-硫代吡啶酮在B-吸收带中的动态结构

doi:10.3866/PKU.WHXB201204173

Abstract

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 π_H→π_L^*, π_H→π_L+1^*, and π_H-1→π_L^* 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

MSC2000:

O641

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[J].Acta Phys. -Chim. Sin., 2012, 28(07): 1570-1578.

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Dynamic Structures of 2-Thiopyrimidone and 2-Thiopyridone in B-Band Absorptions

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