A covalent attraction between two molecular cation TTF·^+  

作　　者：WANG FangFang WANG Yi WANG BingQiang WANG YinFeng MA Fang Li ZhiRu 

机构地区：[1]State Key Laboratory of Theoretical and Computational Chemistry,Institute of Theoretical Chemistry,Jilin University,Changchun 130023,China [2]Basic Course of Public Security Department,China Criminal Police University,Shenyang 110035,China

出　　处：《Science China Chemistry》2009年第11期1980-1986,共7页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20773046)

摘　　要：The optimized structure of the tetrathiafulvalence radical-cation dimer(TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π /π bonding with a telescope shape.The covalent π /π bonding has the bonding energy of about -21 kcal·mol-1 and is concealed by the Coulombic repulsion between two TTF·+ cations.This intermolecular covalent attraction also influences the structure of the TTF·+ subunit,i.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.The optimized structure of the tetrathiafulvalence radical-cation dimer (TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level, which exhibits the attraction between two molecular cation TTF·+. The new attraction interaction is a 20-center-2-electron intermolecular covalent π/π bonding with a telescope shape. The covalent π/π bonding has the bonding energy of about ?21 kcal·mol?1 and is concealed by the Coulombic repulsion between two TTF·+ cations. This intermolecular covalent attraction also influences the structure of the TTF·+ subunit, i.e., its molecular plane is bent by an angle θ = 5.6°. This work provides new knowledge on intermolecular interaction.

关 键 词：radical-cation DIMMER ATTRACTION BETWEEN cations INTERMOLECULAR interaction Π /π bonding TTF 

分 类 号：O641.1[理学—物理化学]