The density functional calculations were used to explore the dissociation energies of [N(CH3)4]+ and [P(CH3)4]+ and their derivatives from substitution of H for CH3.The results show that the dissociation energies of C...The density functional calculations were used to explore the dissociation energies of [N(CH3)4]+ and [P(CH3)4]+ and their derivatives from substitution of H for CH3.The results show that the dissociation energies of C—N and C—P bonds gradually increase as the number of hydrogen atoms bonded to N or P increases in the derivatives,showing a remarkable effect of the intramolecular structural environment on the dissociation of the bonds.This dependence of bond dissociation energies on the local structural environment can be ascribed to the hyperconjugation interactions between the C—H bond and lone single electron of N or P.On the basis of NBO analyses,the bonding properties of dissociated fragments and their effects on dissociation energies were discussed.展开更多
基金supported by the National Natural Science Foundation of China(20973088,21173109,21133005)Specialized Research Fund for the Doctoral Program of Higher Education of China(20102136110001)Program for Liaoning Excellent Talents in University,China(LR2012037)~~
基金supported by the National Natural Science Foundation of China(10804027,11011140321)Natural Science Foundation of Education Department of Henan Province,China(2011A140003)~~
基金supported by the‘XiaoXiang Scholar’Talents Foundation of Hunan Normal University,China (23040609)Hunan Provincial Innovation Foundation for Postgraduate,China (CX2012B223)+1 种基金Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province,ChinaThe Hundred Talents Foundation of Hunan Province is gratefully acknowledged for the financial support to S. J. and S. R. K.~~
文摘The density functional calculations were used to explore the dissociation energies of [N(CH3)4]+ and [P(CH3)4]+ and their derivatives from substitution of H for CH3.The results show that the dissociation energies of C—N and C—P bonds gradually increase as the number of hydrogen atoms bonded to N or P increases in the derivatives,showing a remarkable effect of the intramolecular structural environment on the dissociation of the bonds.This dependence of bond dissociation energies on the local structural environment can be ascribed to the hyperconjugation interactions between the C—H bond and lone single electron of N or P.On the basis of NBO analyses,the bonding properties of dissociated fragments and their effects on dissociation energies were discussed.
