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Absorption Spectra and Photoreactivity of Para-aminobenzophenone by Time-dependent Density Functional Theory
Xue-mei Cheng,Yao Huang,Jian-yi Ma,Xiang-yuan Li*
Author NameAffiliationE-mail
Xue-mei Cheng College of Chemical Engineering, Sichuan University, Chengdu 610065, China  
Yao Huang College of Chemical Engineering, Sichuan University, Chengdu 610065, China  
Jian-yi Ma College of Chemical Engineering, Sichuan University, Chengdu 610065, China  
Xiang-yuan Li* College of Chemical Engineering, Sichuan University, Chengdu 610065, China xyli@scu.edu.cn 
Abstract:
The absorption spectral properties of para-aminobenzophenone (p-ABP) were investigated in gas phase and in solution by time-dependent density functional theory. Calculations suggest that the singlet states vary greatly with the solvent polarities. In various polar solvents, including acetonitrile, methanol, ethanol, dimethyl sulfoxide, and dimethyl formamide, the excited S1 states with charge transfer character result from π→π* transitions. However, in nonpolar solvents, cyclohexane, and benzene, the S1 states are the result of n→π* transitions related to local excitation in the carbonyl group. The excited T1 states were calculated to have ππ* character in various solvents. From the variation of the calculated excited states, the band due to π→π* transition undergoes a redshift with an increase in solvent polarity, while the band due to n→π* transition undergoes a blueshift with an increase in solvent polarity. In addition, the triplet yields and the photoreactivities of p-ABP in various solvents are discussed.
Key words:  TDDFT, p-Aminobenzophenone, Photoreactivity, Excited state
FundProject:
对氨基二苯甲酮光吸收和光反应活性的含时密度泛函研究
程雪梅,黄瑶,马建毅,李象远*
摘要:
利用含时密度泛函理论研究了对氨基二苯甲酮(p-ABP )的气液相吸收光谱性质.结果表明,p-ABP单重态的性质随着溶剂极性的变化发生明显的改变.在极性溶剂乙腈、甲醇、乙醇、二甲亚砜和二甲基甲酰胺中,S1态是产生于π→π*跃迁的电荷转移态;在非极性溶剂环己烷和苯中,S1态是产生于n→π*跃迁的局域激发态.对于p-ABP三重态的计算结果表明,无论是极性溶剂中还是非极性溶剂中T1态都具有π→π*构型.不同溶剂中激发态构型和跃迁能的变化情况表明,对应于n→π*跃迁的吸收光谱随着溶剂极性的增加出现明显的蓝移,对应于π→π*跃迁的吸收光谱则随溶剂极性的增加出现明显红移.通过对计算结果进行分析,讨论了对氨基二苯甲酮三重态量子产率在不同溶剂中的变化情况和它在氢提取反应中表现出低光还原反应活性原因.
关键词:  TDDFT,对氨基二苯甲酮,光反应活性,激发态,氢提取
DOI:10.1088/1674-0068/20/03/273-278
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