A Reinvestigation of the Drimer of para-Benzoquinone and Pyrimidine with MP2, CCSD(T), and DFT Using Functionals Including Those Designed to Describe Dispersion

作者：Marianski Mateusz; Oliva Antoni; Dannenberg J J^*

来源：Journal of Physical Chemistry A, 2012, 116(30): 8100-8105.

DOI：10.1021/jp3050274

We reevaluate the interaction of pyridine and p-benzoquinone using functionals designed to treat dispersion. We compare the relative energies of four different structures: stacked, T-shaped (identified for the first time), and two planar H-bonded geometries using these functionals (B97-D, omega B97x-D, M05, M05-2X, M06, M06L, and M06-2X), other functionals (PBE1PBE, B3LYP, X3LYP), MP2, and CCSD(T) using basis sets as large as cc-pVTZ. The functionals designed to treat dispersion behave erratically as the predictions of the most stable structure vary considerably. MP2 predicts the experimentally observed structure (H-bonded) to be the least stable, while single-point CCSD(T) at the MP2 optimized geometry correctly predicts the observed structure to be the most stable. We have confirmed the assignment of the experimental structure using new calculations of the vibrational frequency shifts previously used to identify the structure. The MP2/cc-pVTZ vibrational calculations are in excellent agreement with the observations. All methods used to calculate the energies provide vibrational shifts that agree with the observed structure even though most do not predict this structure to be most stable. The implications for evaluating possible pi-stacking in biologically important systems are discussed.

• 出版日期2012-8-2