Study of the reactivity of radical-molecular addition reaction using density functional theory  

作　　者：WANG Guichang SHANG Zhenfeng YANG Zuoyin PAN Yinming CAI Zunsheng ZHAO Xuezhuang LI Yongwang SUN Yuhan ZHONG Bing 

机构地区：[1]Department of Chemistry,Nankai University,Tianjin 300071,China [2]Insititute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China

出　　处：《Chinese Science Bulletin》2001年第6期480-482,共3页

基　　金：the Foundation of State Key Laboratory of Coal Conversion.

摘　　要：The reactivity of radical-molecular addition reaction was studied in terms of density-functional theory (DFT) and Hartree-Fock theory (HFT). It was found that the DFT method can give more accurate estimated result than the HFT method. The reason might be that the energy of the highest occupied molecular orbital (HOMO) in DFT is not the ionization energy, but rather represents the change in the total energy with respect to the change in occupation number of electrons in the HOMO, consistent with the concept of the transition state. The energy of HOMO in HFT is the ionization energy, which may represent more properly the property of the products and reactants themselves.The reactivity of radical-molecular addition reaction was studied in terms of density-functional theory (DFT) and Hartree-Fock theory (HFT). It was found that the DFT method can give more accurate estimated result than the HFT method. The reason might be that the energy of the highest occupied molecular orbital (HOMO) in DFT is not the ionization energy, but rather represents the change in the total energy with respect to the change in occupation number of electrons in the HOMO, consistent with the concept of the transition state. The energy of HOMO in HFT is the ionization energy, which may represent more properly the property of the products and reactants themselves.

关 键 词：addition reaction rate CONSTANT density-functional THEORY Hartree-Fock-theory. 

分 类 号：O643.1[理学—物理化学]