针对2-环己烯酮在不同溶剂中紫外吸收谱带发生位移的现象,采用密度泛函理论结合极化连续介质模型(PCM)和自洽等密度表面极化连续介质模型(SCIPCM),研究2-环己烯酮的电子激发光谱及其溶剂效应。结果表明:SCIPCM溶剂模型对2-环己烯酮在非质子性溶剂和质子性溶剂中的电子跃迁能的估算是合适的。计算并指认了2-环己烯酮和2-环己烯酮-(H2O)。簇合物(n=1,2)的紫外光谱,并发现R2簇合物有两个特有电子跃迁带。簇合物的氢键稳定化能计算结果表明R2簇合物是最稳定的构型。R2簇合物的计算光谱与实验光谱基本吻合,说明氢键的相互作用是2-环己烯酮在水中紫外吸收谱带红移的主要原因。
This thesis investigates the electron excitation of 2-cyclohexen-1-one (CHO) and the solvent effects by using density functional theory calculations as well as employing the polarizable continuum mod- el (PCM) and self-consistent isodensity polarizable continuum model (SCIPCM) on the base of the shift of UV absorption spectra of CHO in different solvents. The results show that the SCIPCM solvent model is reasonable for the estimation of electronic transition energies of CHO in aprotic and protic solvents. The authors calculate the UV absorption spectrum of CHO in water and acetonitrile solvents and CHO-(H2O)n clusters (n= 1, 2) in water solvent as well as elucidate and assign the electronic transitions associated with the UV absorptions. Then, the authors discern two electronic transition bands with characteristic CHO- (H20)2 R2 cluster. In addition, the authors estimate the stabilized energies for CHO-(H2O), clusters (n =1, 2) and find that CHO-(H2O)2 R2 cluster is the most stable one. The calculated spectrum of CHO- (H2O)2 R2 cluster basically agrees with that of experimental measurement which indicates that hydrogen bonds interaction is the main reason for the red shift of UV absorption spectrum of CHO in water solvent.