How accurate is the density functional theory combined with symmetry-adapted perturbation theory approach for CH-pi and pi-pi interactions? A comparison to supermolecular calculations for the acetylene-benzene dimer.
Five different orientations of the acetylene-benzene dimer including the T-shaped global minimum structure are used to assess the accuracy of the density functional theory combined with symmetry adapted perturbation theory (DFT-SAPT) approach in its density-fitting implementation (DF-DFT-SAPT) for the study of CH-pi and pi-pi interactions. The results are compared with the outcome of counterpoise corrected supermolecular calculations employing second-order Møller-Plesset (MP2), spin-component scaled MP2 (SCS-MP2) and single and double excitation coupled cluster theory including perturbative triple excitations (CCSD(T)). For all considered orientations MP2 predicts much deeper potential energy curves with considerably shifted minima compared to CCSD(T) and DFT-SAPT. In spite of being an improvement over the results of MP2, SCS-MP2 tends to underestimate the well depth while DFT-SAPT, employing an asymptotically corrected hybrid exchange-correlation potential in conjunction with the adiabatic local density approximation for the exchange-correlation kernel, is found to be in excellent agreement with CCSD(T). Furthermore, DFT-SAPT provides a detailed understanding of the importance of the electrostatic, induction and dispersion contributions to the total interaction energy and their repulsive exchange corrections.
Tekin
Adem
A
Fachbereich Chemie, Universität Duisburg-Essen, Universitätsstrasse 5, 45117, Essen, Germany.
Jansen
Georg
G
D000480:Alkynes / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry*; D019281:Dimerization; D008956:Models, Chemical; D011789:Quantum Theory
D000480:Alkynes; D001554:Benzene