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Theoretical Study on Intermolecular Interactions and Thermodynamic Properties of Nitroamine Dimers
Author(s) -
Ju XueHai,
Xiao HeMing
Publication year - 2002
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20020200305
Subject(s) - chemistry , dimer , intermolecular force , ab initio , basis set , binding energy , monomer , thermodynamics , computational chemistry , gibbs free energy , force field (fiction) , trimer , interaction energy , crystallography , molecule , density functional theory , atomic physics , polymer , organic chemistry , physics , artificial intelligence , computer science
Ab initio self‐consistent field (SCF) and Møller‐Plesset correlation correction methods employing 6‐31G* * basis set have been applied to the optimizations of nitroamine dimers. The binding energies have been corrected for the basis set superposition error (BSSE) and the zero‐point energy. Three optimized dimers have been obtained. The BSSE corrected binding energy of the most stable dimer is predicted to be ‐31.85 kJ/mol at the MP4/6‐31G* * /MP2/6‐31G* * level. The energy barriers of the Walden conversion for ‐ NH 2 group are 19.7 kJ/mol and 18.3 kJ/mol for monomer and the most stable dimer, respectively. The molecular interaction makes the internal rotation around N 1 ‐ N 2 even more difficult. The thermodynamic properties of nitroamine and its dimers at different temperatures have been calculated on the basis of vibrational analyses. The change of the Gibbs free energy for the aggregation from monomer to the most stable dimer at standard pressure and 298.2 K is predicted to be 14.05 kJ/mol.