Theoretical Study on Intermolecular Interactions and Thermodynamic Properties of Dimethylnitroamine Clusters

Ab initio SCF and Mφller-Plesset correlation correction methods in combination with counterpose procedure for BSSE correction have been applied to the theroetical studying of dimethylnitroamine and its dimers and trimers.Three optimized stable dimers and two trimers have been obtained.The corrected binding energies of the most stable dimer and trimer were predicted to be -24.68kJ/mol and -47.27kJ/mol,respectively at the MP2/6-31G^*//HF/6-31G^* level.The proportion of correlated interation energies to their total interaction energies for all clusters was at least 29.3 percent,and the BSSE of ΔE(MP2) was at least 10.0kJ/mol.Dispersion and/or electrostatic force were dominant in all clusters.There exist cooperative effects in both the chain and the cyclic trimers.The vibrational frequencies associated with N-O stretches or wags exhibit slight red shifts,but the modes associated with the motion of hydrogen atoms of the methyl group show somewhat blue shifts with respect to those of monomer.Thermodynamic properties of dimethylnitroamine and its clusters at different temperatures have been calculated on the basis of vibrational analyses.The changes of the Gibbs free energies for the aggregation from monomer to the most stable dimer and trimer were predicted to be 14.37kJ/mol and 30.40kJ/mol,respectively,at 1 atm and 298.15K.

Theoretical Study on Intermolecular Interactions and Thermodynamic Properties of Dimethylnitroamine Clusters

Ab initio SCF and Møller‐Plesset correlation correction methods in combination with counterpoise procedure for BSSE correction have been applied to the theoretical studying of dimethylnitroamine and its dimers and trimers. Three optimized stable dimers and two trimers have been obtained. The corrected binding energies of the most stable dimer and trimer were predicted to be ? 24.68 kJ/mol and ? 47.27 kJ/mol, respectively at the MP2/6‐31G*//F/6‐31G* level. The proportion of correlated interaction energies to their total interaction energies for all clusters was at least 29.3 percent, and the BSSE of ΔE(MP2) was at least 10.0 kJ/mol. Dispersion and/or electrostatic force were dominant in all clusters. There exist cooperative effects in both the chain and the cyclic trimers. The vibrational frequencies associated with N—O stretches or wags exhibit slight red shifts, but the modes associated with the motion of hydrogen atoms of the methyl group show somewhat blue shifts with respect to those of monomer. Thermodynamic properties of dimethylnitroamine and its clusters at different temperatures have been calculated on the basis of vibrational analyses. The changes of the Gibbs free energies for the aggregation from monomer to the most stable dimer and trimer were predicted to be 14.37 kJ/mol and 30.40 kJ/mol, respectively, at 1 atm and 298.15 K.