Ab initio Calculations of Protonated Ethylenediamine-(water)3 Complex: Roles of Intramolecular Hydrogen Bonding and Hydrogen Bond Cooperativity

Ab initio Calculations of Protonated Ethylenediamine-(water)3 Complex: Roles of Intramolecular Hydrogen Bonding and Hydrogen Bond Cooperativity

Ab initio density functional calculations on the structural isomers, the hydration energies, and the hydrogen bond many-body interactions for gauche-, trans-protonated ethylenediamine-(water)3 complexes (g-enH+(H2O)3, t-enH+(H2O)3) have been performed. The structures and relative stabilities of three representative isomers (cyclic, tripod, open) between g-enH+(H2O)3 and t-enH+(H2O)3 are predicted to be quite different due to the strong interference between intramolecular hydrogen bonding and water hydrogen bond networks in g-enH+(H2O)3. Many-body analyses revealed that the combined repulsive relaxation energy and repulsive nonadditive interactions for the mono-cyclic tripod isomer, not the hydrogen bond cooperativity, are mainly responsible for the greater stability of the bi-cyclic isomer.