Density functional theory（DFT） calculations are performed to investigate the reactivity of Th atom toward ethane C–C bond activation.A comprehensive description of the reaction mechanisms leading to two different r...Density functional theory（DFT） calculations are performed to investigate the reactivity of Th atom toward ethane C–C bond activation.A comprehensive description of the reaction mechanisms leading to two different reaction products is presented.We report a complete exploration of the potential energy surfaces by taking into consideration different spin states.In addition,the intermediate and transition states along the reaction paths are characterized.Total,partial,and overlap population density of state diagrams and analyses are also presented.Furthermore,the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function（ELF） and Mayer bond order.Infrared spectrum（IR） is obtained and further discussed based on the optimized geometries.展开更多
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths.Building on our recent work,in this paper we add further evidence on the...Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths.Building on our recent work,in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis.Presently reported results include atomic charges,natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC_(2k/2k+1)H chain family.They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes,e.g.,electron removal from or electron attachment to a neutral chain.Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC_(2k/2k+1)H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21371160,21401173,and 11364023)
文摘Density functional theory（DFT） calculations are performed to investigate the reactivity of Th atom toward ethane C–C bond activation.A comprehensive description of the reaction mechanisms leading to two different reaction products is presented.We report a complete exploration of the potential energy surfaces by taking into consideration different spin states.In addition,the intermediate and transition states along the reaction paths are characterized.Total,partial,and overlap population density of state diagrams and analyses are also presented.Furthermore,the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function（ELF） and Mayer bond order.Infrared spectrum（IR） is obtained and further discussed based on the optimized geometries.
基金financial support from the German Research Foundation(DFG Grant No.BA 1799/3-2)in the initial stage of this work and computational support by the state of Baden-Württemberg through bw HPC and the German Research Foundation through Grant No.INST 40/575-1 FUGG(bw Uni Cluster 2.0,bw For Cluster/MLS&WISO 2.0/HELIX,and JUSTUS 2.0 cluster)
文摘Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths.Building on our recent work,in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis.Presently reported results include atomic charges,natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC_(2k/2k+1)H chain family.They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes,e.g.,electron removal from or electron attachment to a neutral chain.Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC_(2k/2k+1)H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.
