Molecular Tailoring Approach for Estimating Individual Intermolecular Interaction Energies in Benzene Clusters

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.

Unusually Large Hydrogen-Bond Cooperativity in Hydrogen Fluoride Clusters, (HF)n,n= 3 to 8, Revealed by the Molecular Tailoring Approach

“…In this work, the individual F–H···F HB energy and cooperativity contributions in linear (L) and cyclic (C) hydrogen fluoride (HF) n , n = 3–8 clusters, are reported. For this purpose, we have applied our recently proposed MTA-based methodology. − The HB energies in these L-(HF) n clusters ( n = 3 to 8) falls between 6.2 to 9.5 kcal/mol and the cooperativity contributions are between 1.0 (about 16%) and 4.8 kcal/mol (about 50%). In the case of C-(HF) n clusters ( n = 3 to 8), the HB energies are between 7.9 to 11.4 kcal/mol.…”

“…In the recent past, a fragmentation-based method for the estimation of individual intramolecular hydrogen-bond energy (IHBE) in a variety of systems was proposed by Deshmukh and Gadre. − This methodology has been extended for estimating the individual HB energy and cooperativity in water (W n ) and ammonia clusters (NH 3 ) n and also for the energies of individual intermolecular interactions in benzene (Bz) n clusters. With the aim of exploring the strong associative interconnected network of HBs in HF clusters, in this work, we study some linear (L) and cyclic (C) hydrogen fluoride (HF) n clusters employing our molecular tailoring approach (MTA)-based method. − …”

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

“…water (W n ), [39] ammonia (NH 3 ) n , [40] hydrogen fluoride (HF) n [41] and mixed (HF) m -(W) n [42] clusters. They also applied this method for the individual intermolecular interaction energies in benzene (Bz) n [43] clusters.…”

“…water (W n ), [39] ammonia (NH 3 ) n , [40] hydrogen fluoride (HF) n [41] and mixed (HF) m (W) n [42] clusters. They also applied this method for the individual intermolecular interaction energies in benzene (Bz) n [43] clusters. The calculated HB energies in W n clusters, for n=3 to 8, lie in the wide range of 0.3 to 11.6 kcal mol −1 at MP2(full)/aug‐cc‐pVTZ level [39] …”

Molecular tailoring approach as tool for revealing resonance‐assisted hydrogen bond: Case study of Z‐pyrrolylenones with the NH⋯OС intramolecular hydrogen bond

“…One of the most advanced methods to quantify the IMHB energy is the molecular tailoring approach (MTA) 45–47 . Moreover, this method is effectively used not only to evaluate the IMHB energy in medium and large molecules, 48–61 but also to assess the energy of intermolecular hydrogen bonds in large molecular clusters 62–66 . Based on the MTA method, the following methodology can be used to establish the nature of H‐bond in the pyrrolylenones (i.e.…”