Theoretical Analysis of an Anion-πComplex:I-·C6F6  

阴离子-π复合物(I-·C6F6)的成键分析

作　　者：Zhang-yun Liu Zheng Chen Xin Xu 刘章云;陈征;徐昕(能源材料化学协同创新中心,上海市分子催化和功能材料重点实验室,物质计算科学教育部重点实验室,复旦大学化学系,上海200433)

机构地区：[1]Collaborative Innovation Center of Chemistry for Energy Materials,Shanghai Key Laboratory of Molec-ular Catalysis and Innovative Materials,MOE Key Laboratory of Computational Physical Sciences,Department of Chemistry,Fudan University,Shanghai 200433,China

出　　处：《Chinese Journal of Chemical Physics》2020年第3期285-290,I0002,共7页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21688102 and No.91027044)。

摘　　要：Recently,AnstÖter and co-workers[J.Am.Chem.Soc.141,6132(2019)]have provided the first photoelectron spectroscopic determination of the anion-πbond strength(De)using iodide-hexafluorobenzene(I-·C6F6)as the archetypical system.In combination with an equation-of-motion coupled cluster theory,namely EOM-IP-CCSD(d T),using Dunning’s aug-cc-p VDZ(a VDZ)basis set,Dein I-·C6F6 was found to be-0.53 e V with an uncertainty less than±0.03 e V.The interaction was claimed to arise for a large part from correlation forces(41%)with only a 23%contribution from electrostatic forces.In the present work,we performed the coupled-cluster with single and double and perturbative triple excitations,CCSD(T),calculations.We found that CCSD(T)/a VDZ can have an uncertainty up to 0.113 e V due to the basis set incompleteness.Our calculations disclosed that the previous calculations on the electrostatic contribution are concealed by the contributions from the exchange and Pauli repulsion.The electrostatic contribution is actually determinant,being more than double of the correlation contribution in the I-·C6F6 complex at the equilibrium binding distance.

关 键 词：Anion-πinteractions I-·C6F6 Electrostatic interaction Correlation OEE XYG3 CCSD(T) 

分 类 号：O641.1[理学—物理化学]