Symmetry-Adapted Perturbation-Theory Interaction-Energy Decomposition for Hydrogen-Bonded and Stacking Structures

摘要

This letter reports the computational ab initio studies on the stacked and hydrogen-bonded geometries of the uracil dimer and pyrimidine···p-benzoquinone complex with a special regard to the ratios of different interaction-energy terms calculated by means of the symmetry-adapted perturbation theory (SAPT). In the hydrogen-bonded systems the absolute value of the dispersion term constitutes approximately half of the absolute value of the total SAPTO interaction energy, while in the stacking complexes the ratio of the dispersion to the total interaction energy is much larger, ca. 1.2-2.0. Our SAPT results are compared with the DFT-SAPT results published recently by the Hobza group (J. Chem. Phys. 2007, 127, 075104), and the role of the dispersion contribution in stacking and hydrogen-bonded arrangements is discussed. The methodological part of this letter presents the influence of counterpoise corrections in the optimization procedure on the geometries of the systems and the calculated SAPT contributions.