Zeinalipour-Yazdi, Constantinos D. ORCID: 0000-0002-8388-1549 and Pullman, David P. (2006) Correlation of polarizabilities with van der Waals interactions in pi-systems. The Journal of Physical Chemistry B, 110 (47). pp. 24260-24265. ISSN 1520-6106 (Print), 1520-5207 (Online) (doi:https://doi.org/10.1021/jp064681h)

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Abstract

This work aims to (i) provide a semiquantitative relationship that can be used to estimate the binding energy, equilibrium separation, and potential energy surface (PES) for supermolecules consisting of benzene and small polycyclic aromatic hydrocarbons (PAHs) in parallel configuration and (ii) give a qualitative description of π−π interactions between PAHs. We compute the one-dimensional PES of benzene translated parallel to various PAHs within the framework of second-order Møller−Plesset (MP2) perturbation theory. For PAHs of small MW difference, we observe a linear correlation between the binding energy and the number of carbon atoms in the supermolecule. The PES of these supermolecules is fit to an (exp-6) function whose variables are subsequently used to derive a mass-centered potential energy function as a function of the number of carbon atoms in the supermolecule. The linear dependence of the binding energy in the supermolecular series examined here can be directly correlated to the average polarizability product of the supermolecule. Last, we consider the supermolecular series of benzene with n-polyacenes to study the convergence of π−π interactions between PAHs when their size is considerably different.

Item Type:	Article
Uncontrolled Keywords:	VdW, DFT, PAH, polarizability
Subjects:	Q Science > QD Chemistry
Faculty / School / Research Centre / Research Group:	Faculty of Engineering & Science Faculty of Engineering & Science > School of Science (SCI)
Last Modified:	06 Oct 2018 23:56
URI:	http://gala.gre.ac.uk/id/eprint/21460

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