采用密度泛函理论B3P86方法,在6-31G(d,p)基组水平上,对木质素结构中的6种连接方式(β-O-4、α-O-4、4-O-5、β-1、α-1、5-5)的63个木质素模化物的醚键(C-O)和C-C键的键离解能EB进行了理论计算研究。分析了不同取代基对键离解能的影响...采用密度泛函理论B3P86方法,在6-31G(d,p)基组水平上,对木质素结构中的6种连接方式(β-O-4、α-O-4、4-O-5、β-1、α-1、5-5)的63个木质素模化物的醚键(C-O)和C-C键的键离解能EB进行了理论计算研究。分析了不同取代基对键离解能的影响以及键长与键离解能的相关性。计算结果表明,C-O键的键离解能通常比C-C键的小,在各种醚键中Cα-O键的平均键离解能最小,为182.7 k J/mol;其次是β-O-4连接中的Cβ-O键,苯环和烷烃基上的取代基对醚键的键离解能有较强的弱化作用,C-O键的键长和键离解能的相关性较差。与C-O键相比,C-C键的键离解能受苯环上取代基的影响很小,而烷烃基上的取代基对C-C键的键离解能有较大的影响,C-C键的键离解能和键长之间存在较强的线性关系,C-C键的键长越长,其键离解能越小。展开更多
Configuration interaction tenichque is applied to the valence bond theory. Virtual VB orbitals are built, which are localized and orthogonal to their corresponding occupied orbitals and the excited VB structures are d...Configuration interaction tenichque is applied to the valence bond theory. Virtual VB orbitals are built, which are localized and orthogonal to their corresponding occupied orbitals and the excited VB structures are defined, which come from their corresponding fundamental VB structures. The testing calculations of H 2, LiH, HF show that the VB results using CI method match those of the molecular orbital based on the coupled cluster CCSD method, and the CI technique may become a useful tool in VB method.展开更多
文摘采用密度泛函理论B3P86方法,在6-31G(d,p)基组水平上,对木质素结构中的6种连接方式(β-O-4、α-O-4、4-O-5、β-1、α-1、5-5)的63个木质素模化物的醚键(C-O)和C-C键的键离解能EB进行了理论计算研究。分析了不同取代基对键离解能的影响以及键长与键离解能的相关性。计算结果表明,C-O键的键离解能通常比C-C键的小,在各种醚键中Cα-O键的平均键离解能最小,为182.7 k J/mol;其次是β-O-4连接中的Cβ-O键,苯环和烷烃基上的取代基对醚键的键离解能有较强的弱化作用,C-O键的键长和键离解能的相关性较差。与C-O键相比,C-C键的键离解能受苯环上取代基的影响很小,而烷烃基上的取代基对C-C键的键离解能有较大的影响,C-C键的键离解能和键长之间存在较强的线性关系,C-C键的键长越长,其键离解能越小。
文摘Configuration interaction tenichque is applied to the valence bond theory. Virtual VB orbitals are built, which are localized and orthogonal to their corresponding occupied orbitals and the excited VB structures are defined, which come from their corresponding fundamental VB structures. The testing calculations of H 2, LiH, HF show that the VB results using CI method match those of the molecular orbital based on the coupled cluster CCSD method, and the CI technique may become a useful tool in VB method.
