%A 曲瑞娟;石佳奇;程润秋;杨 曦;王遵尧
%T DFT Study on Some Properties of Polybrominated Phenoxathiin 10-Oxides
%0 Journal Article
%D 2011
%J 结构化学
%R
%P 1501-1508
%V 30
%N 10
%U {http://manu30.magtech.com.cn/jghx/CN/abstract/article_442.shtml}
%8
%X With the B3LYP calculation method of density functional theory (DFT) and the 6-31G* basis set, full optimization calculation was made for phenoxathiin10-oxide (PTO) and 135 polybromine phenoxathiin 10-oxides (PBPTOs) with the Gaussian 03 program and molar heat capacity in constant volume (C_{V}^{θ}) value of each molecule in the standard state was obtained. The relation between C_{V}^{θ} and the substitution position and number of bromine atom (*N*_{PBS}) was studied, and the results indicated good correlation (*R*^{2} = 1.000) between C_{V}^{θ} and *N*_{PBS} of PBPTO compounds. Based on the out_{p}ut file of Gaussian 03 progr_{a}m, mol_{a}r heat capacity at constant pressure (*C*_{p,m}) of PBPTO compounds from 200 to 1,000 K was calculated with the statistical thermodynamics program, and the correlation equation between *C*_{p,m} and temperature (*T*, *T*^{-1} and *T*^{-2}) was obtained with the least-squares method, and the correlation coefficient of the correlation equation (*R*^{2}) was 1.000. In addition, based on the partition function of each molecule calculated by vibration analysis, the relative rate constant of formation of each molecule was calculated.