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Searching of potential energy curves for the benzene dimer using dispersion-corrected density functional theory†
Prakash Chandra Jha,Zilvinas Rinkevicius,Hans Ågren,Prasenjit Seal,Swapan Chakrabarti
Physical Chemistry Chemical Physics Pub Date : 02/26/2008 00:00:00 , DOI:10.1039/B717983A
Abstract

The present work aims to establish the utility of dispersion-corrected density functional theory for potential energy curves of the benzene dimer, a problem that has received significant attention for a long time. The interaction energies of parallel-stacked, T-shaped and parallel-displaced benzene dimer configurations have been evaluated using both dispersion- and normal gradient-corrected Perdew–Burke–Ernzerhof functionals along with Dunning’s augmented correlation-consistent polarized valence triple-zeta (aug-cc-pVTZ) basis functions and compared with explicit correlation methods. The potential energy curves for the parallel-stacked and parallel-displaced benzene dimers are in excellent agreement with highly accurate coupled cluster (CCSD(T)) results, while for the T-shaped benzene dimer the dispersion-corrected results show a distinct deviation, being closer in that case to the MP2 level of results. The overestimation of interaction energy in the T-shaped dimer may be attributed to the presence of a permanent dipole moment in this configuration and indicates a structural dependence of the dispersion-corrected density functional method.

Graphical abstract: Searching of potential energy curves for the benzene dimer using dispersion-corrected density functional theory
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