Searching of potential energy curves for the benzene dimer using dispersion-corrected density functional theory.
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.
Jha
Prakash Chandra
PC
Department of Theoretical Chemistry, School of Biotechnology, Royal Institute of Technology, Stockholm, Sweden. prakash@theochem.kth.se
Rinkevicius
Zilvinas
Z
Agren
Hans
H
Seal
Prasenjit
P
Chakrabarti
Swapan
S
D001554:Benzene / Q000737:chemistry*; D019281:Dimerization; D008958:Models, Molecular
D001554:Benzene