Quantum chemical topological analysis of hydrogen bonding in HX…HX and CH3X…HX dimers (X = Br, Cl, F)

We present a systematic investigation of the nature and strength of the hydrogen bonding in HX···HX and CH3X…HX (X = Br, Cl and F) dimers using ab initio MP2/aug-cc-pVTZ calculations in the framework of the quantum theory of atoms in molecules (QTAIM) and electron localisation functions (ELFs) methods. The electron density of the complexes has been characterised, and the hydrogen bonding energy, as well as the QTAIM and ELF parameters, is consistent, providing deep insight into the origin of the hydrogen bonding in these complexes. It was found that in both linear and angular HX…HX and CH3X…HX dimers, F atoms form stronger HB than Br and Cl, but they need short (∼2 Å) X…HX contacts.The authors are grateful to FAPESP and FAPEMIG for financially supporting this research and for a scholarship (to R.A.C.), to CAPES for the scholarships (to F.A.L. and R.T.S.) and to CNPq for the fellowships (to T.C.R., M.P.F., E.F.F.C. and R.R.). J.A. also thanks Universitat Jaume I-Fundacio´n Bancaixa (Project P1.1B2010-10), Generalitat Valenciana for Prometeo/2009/053 project, Ministerio de Ciencia e Innovacio´n for project CTQ2009-14541-C02 and Programa de Cooperacio´n Cientı´fica con Iberoamerica (Brazil), Ministerio de Educacio´n (PHB2009-0065-PC)