title: A B3LYP and MP2(full) theoretical investigation into the cooperativity effect between dihydrogen-bonding and H-M∙∙∙π (M = Li, Na, K) interactions among HF, MH with the π-electron donor C2H2, C2H4 or C6H6.
abstract: The DFT-B3LYP/6-311++G(3df,2p) and MP2(full)/6-311++G(3df,2p) calculations were carried out on the binary complex formed by HM (M = Li, Na, K) and HF or the π-electron donor (C2H2, C2H4, C6H6), as well as the ternary system FH∙∙∙HM∙∙∙C2H2/C2H4/C6H6. The cooperativity effect between the dihydrogen-bonding and H-M∙∙∙π interactions was investigated. The result shows that the equilibrium distances R(H∙∙∙H) and R(M∙∙∙π) in the ternary complex decrease and both the H∙∙∙H and H-M∙∙∙π interactions are strengthened when compared to the corresponding binary complex. The cooperativity effect of the dihydrogen bond on the H-M∙∙∙π interaction is more pronounced than that of the M∙∙∙π bond on the H∙∙∙H interaction. Furthermore, the values of cooperativity effect follow the order of FH∙∙∙HNa∙∙∙π > FH∙∙∙HLi∙∙∙π > FH∙∙∙HK∙∙∙π and FH∙∙∙HM∙∙∙C6H6 > FH∙∙∙HM∙∙∙C2H4 > FH∙∙∙HM∙∙∙C2H2. The nature of the cooperativity effect was revealed by the analyses of the charge of the hydrogen atoms in H∙∙∙H moiety, atom in molecule (AIM) and electron density shifts methods.
authors.affiliation: College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China.
authors.forename: Jian-feng
authors.initials: JF
authors.lastname: Guo
authors.forename: Wen-jing
authors.initials: WJ
authors.lastname: Shi
authors.forename: Fu-de
authors.initials: FD
authors.lastname: Ren
authors.forename: Duan-lin
authors.initials: DL
authors.lastname: Cao
authors.forename: Yuan-sheng
authors.initials: YS
authors.lastname: Zhang
mesh_terms: D002414:Cations, Monovalent; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D011188:Potassium / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D002414:Cations, Monovalent; D006859:Hydrogen; D008094:Lithium; D012964:Sodium; D011188:Potassium