BSSE-free hardness profiles of hydrogen bond exchange in the hydrogen fluoride dimer

摘要

Hardness profiles are calculated for the hydrogen bond interchange in the hydrogen fluoride dimer; the study is carried out at the Hartree-Fock and second-order Moller-Plesset (MP2) levels of theory with three different basis sets. The basis set superposition error (BSSE) is corrected by means of the chemical Hamiltonian approach (CHA). Uncorrected and BSSE-corrected energy and hardness profiles are compared. Their analysis shows that hardness profiles do not lead to spurious minima as energy profiles do in various cases. The CHA methodology is shown to be valuable in the analysis of intermolecular interactions, with BSSE observed to carry smaller modifications on hardness profiles than on energy curves. (C) 2006 Wiley Periodicals, Inc.