摘要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.

Abstract：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.

曲瑞娟;石佳奇;程润秋;杨 曦;王遵尧. DFT Study on Some Properties of Polybrominated Phenoxathiin 10-Oxides[J]. , 2011, 30(10): 1501-1508.
QU Rui-Juan;SHI Jia-Qi;CHENG Run-Qiu;YANG Xi;WANG Zun-Yao. DFT Study on Some Properties of Polybrominated Phenoxathiin 10-Oxides. , 2011, 30(10): 1501-1508.