Molecular Tailoring Approach for Estimating Individual Intermolecular Interaction Energies in Benzene Clusters
Mini Bharati Ahirwar, Nalini D. Gurav, Shridhar R. Gadre, Milind M. Deshmukh
Abstract
There is no general method available for the estimation of individual intermolecular interaction energies in weakly bound molecular clusters, and such studies are limited only to the dimer. Recently, we proposed a molecular tailoring approach-based method for the estimation of individual O–H···O hydrogen bond energies in water clusters. In the present work, we extend the applicability of this method for estimating the individual intermolecular interaction energies in benzene clusters, which are expected to be small. The basis set superposition error (BSSE)-corrected individual intermolecular interaction energies in linear (LN) benzene clusters, LN-(Bz)n n = 3–7, were calculated to be in the range from −1.75 to −2.33 kcal/mol with the cooperativity contribution falling between 0.05 and 0.20 kcal/mol, calculated at the MP2.5/aug-cc-pVDZ level of theory. In the case of non-linear (NLN) benzene clusters, NLN-(Bz)n n = 3–5, the BSSE-corrected individual intermolecular interaction energies exhibit a wider range from −1.16 to −2.55 kcal/mol with cooperativity contribution in the range from 0.02 to −0.61 kcal/mol. The accuracy of these estimated values was validated by adding the sum of interaction energies to the sum of monomer energies. These estimated molecular energies of clusters were compared with their actual calculated values. The small difference (<0.3 kcal/mol) in these two values suggests that our estimated individual intermolecular interaction energies in benzene clusters are quite reliable.