J. Phys. Chem. A 115, 12677-12687 (2011)

DOI: 10.1021/jp203576j

Ab Initio Study of Ternary Complexes X:(HCNH)+:Z with X, Z = NCH, CNH, FH, ClH, and FCl: Diminutive Cooperative Effects on Structures, Binding Energies, and Spin-Spin Coupling Constants Across Hydrogen Bonds

Ab initio calculations have been performed on a series of complexes in which (HCNH)+ is the proton donor and CNH, NCH, FH, ClH, and FCl (molecules X and Z) are the proton acceptors in binary complexes X:HCNH+ and HCNH+:Z, and ternary complexes X:HCNH+:Z. These complexes are stabilized by C–H+···A and N–H+···A hydrogen bonds, where A is the electron-pair donor atom of molecules X and Z. Binding energies of the ternary complexes are less than the sum of the binding energies of the corresponding binary complexes. In general, as the binding energy of the binary complex increases, the diminutive cooperative effect increases. The structures of these complexes, data from the AIM analyses, and coupling constants 1J(N–H), 1hJ(H–A), and 2hJ(N–A) for the N–H+···A hydrogen bonds, and 1J(C–H), 1hJ(H–A), and2hJ(C–A) for the C–H+···A hydrogen bonds provide convincing evidence of diminutive cooperative effects in these ternary complexes. In particular, the symmetric N···H+···N hydrogen bond in HCNH+:NCH looses proton-shared character in the ternary complexes X:HCNH+:NCH, while the proton-shared character of the C···H+···C hydrogen bond in HNC:HCNH+ decreases in the ternary complexes HNC:HCNH+:Z and eventually becomes a traditional hydrogen bond as the strength of the HCNH+···Z interaction increases.