Calculation of intermolecular interactions in the benzene dimer using coupled-cluster and local electron correlation methods

Hill, J.G., Platts, J.A. and Werner, H.-J. (2006) Calculation of intermolecular interactions in the benzene dimer using coupled-cluster and local electron correlation methods. Physical Chemistry Chemical Physics, 8(35), pp. 4072-4078. (doi: 10.1039/b608623c)

Abstract

Potential energy curves for the parallel-displaced, T-shaped and sandwich structures of the benzene dimer are computed with density fitted local second-order Møller–Plesset perturbation theory (DF-LMP2) as well as with the spin-component scaled (SCS) variant of DF-LMP2. While DF-LMP2 strongly overestimates the dispersion interaction, in common with canonical MP2, the DF-SCS-LMP2 interaction energies are in excellent agreement with the best available literature values along the entire potential energy curves. The DF-SCS-LMP2 dissociation energies for the three structures are also compared with new complete basis set estimates of the interaction energies obtained from accurate coupled cluster (CCSD(T)) and DF-SCS-MP2 calculations. Since LMP2 is essentially free of basis set superposition errors, counterpoise corrections are not required. As a result, DF-SCS-LMP2 is computationally inexpensive and represents an attractive method for the study of larger π-stacked systems such as truncated sections of DNA.

• Item Type: Articles (Other)
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Hill, Dr John
• Authors: Hill, J.G., Platts, J.A., and Werner, H.-J.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Physical Chemistry Chemical Physics
• Publisher: Royal Society of Chemistry
• ISSN: 1463-9076
• Published Online: 27 July 2006