Abstract：Raman spectra of acetone’s carbonyl stretching in 16 solvents were measured, and were also calculated by self-consistent reaction field (SCRF) method in Gaussian03. The frequency shift in experiment was analyzed by donor-acceptor model, Kirkwood model and SCRF model respectively. Among them, the donor-acceptor model can explain the shift very well. The SCRF method can do it also, while not as well as the donor-acceptor model, but is better than Kirkwood model. Correlating the mechanisms of the 3 methods, it was found that the donor-acceptor model is powerful in explaining the vibrational spectra of molecular bond, which is nucleophilic reagent. The SCRF model considers not only the influence of dielectric constant ε, but also the influence of the bulk and the structure of molecule etc. Although the model is complex and difficult to calculate, but it takes many factors into account, so the calculated results accord with experiment better than the Kirkwood model. The main parameter of the Kirkwood model is ε, so it is very simple and easy to calculate, nonetheless the trend of frequency shift can still be reflected, indicating that the dielectric constant ε is a main character affecting the frequency shift.
Key words：Donor-acceptor model;Solvent effect;Kirkwood model;SCRF model
黄保坤,任春年,里佐威*,李占龙,李兆凯,陆国会. 丙酮CO键在溶剂中频移变化的几种理论模型比较[J]. 光谱学与光谱分析, 2007, 27(10): 1942-1944.
HUANG Bao-kun, REN Chun-nian, LI Zuo-wei*, LI Zhan-long, LI Zhao-kai, LU Guo-hui. Explanation of CO of Acetone Changing in Solvents by Some Models. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(10): 1942-1944.
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