Premium
Ab Initio Study on Interactions in Difluoroamine Clusters from one to four Molecules
Author(s) -
Ju XueHai,
Xiao HeMing
Publication year - 2002
Publication title -
propellants, explosives, pyrotechnics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.56
H-Index - 65
eISSN - 1521-4087
pISSN - 0721-3115
DOI - 10.1002/prep.200290001
Subject(s) - trimer , tetramer , dimer , counterpoise , ab initio , intermolecular force , chemistry , molecule , crystallography , interaction energy , basis set , computational chemistry , exothermic process , ab initio quantum chemistry methods , exothermic reaction , density functional theory , adsorption , organic chemistry , enzyme
Abstract Ab initio calculations at HF, MP2 levels of theory with 6‐311G* basis set in combination with counterpoise procedure for BSSE correction have been performed on difluoroamine clusters consisting of up to four molecules. The dimer, trimer and tetramer were all found to exhibit two minima. There are two types of clusters: cyclic and chain. The corrected bond energies are 9.19, 19.22 and 33.67 kJ/mol at the MP2/6‐311G*//HF/6‐311G* level for the more stable dimer, trimer and tetramer, respectively. The contribution of cooperative effect to the interaction energy is quite significant in the cyclic clusters, but negligible in the chain ones. There exist H‐bonds which involve six and eight F⋅⋅⋅H contacts at ca. 0.23–0.24 nm in cyclic trimer and cyclic tetramer, respectively. The intermolecular interaction is an exothermic process under 400.0 K accompanied by a decrease in the probability of complex formation, and the interactions become weak as temperature increases.