Small and Efficient Basis Sets for the Evaluation of Accurate Interaction Energies: Aromatic Molecule鈥揂rgon Ground-State Intermolecular Potentials and Rovibrational States

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• 作者：Hubert Cybulski ; Angelika Baranowska-艁膮czkowska ; Christian Henriksen ; Berta Fern谩ndez
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：November 6, 2014
• 年：2014
• 卷：118
• 期：44
• 页码：10288-10297
• 全文大小：429K
• ISSN：1520-5215

文摘

By evaluating a representative set of CCSD(T) ground state interaction energies for van der Waals dimers formed by aromatic molecules and the argon atom, we test the performance of the polarized basis sets of Sadlej et al. (J. Comput. Chem. 2005, 26, 145; Collect. Czech. Chem. Commun. 1988, 53, 1995) and the augmented polarization-consistent bases of Jensen (J. Chem. Phys. 2002, 117, 9234) in providing accurate intermolecular potentials for the benzene鈥? naphthalene鈥? and anthracene鈥揳rgon complexes. The basis sets are extended by addition of midbond functions. As reference we consider CCSD(T) results obtained with Dunning鈥檚 bases. For the benzene complex a systematic basis set study resulted in the selection of the (Z)Pol-33211 and the aug-pc-1-33321 bases to obtain the intermolecular potential energy surface. The interaction energy values and the shape of the CCSD(T)/(Z)Pol-33211 calculated potential are very close to the best available CCSD(T)/aug-cc-pVTZ-33211 potential with the former basis set being considerably smaller. The corresponding differences for the CCSD(T)/aug-pc-1-33321 potential are larger. In the case of the naphthalene鈥揳rgon complex, following a similar study, we selected the (Z)Pol-3322 and aug-pc-1-333221 bases. The potentials show four symmetric absolute minima with energies of 鈭?83.2 cm^鈥? for the (Z)Pol-3322 and 鈭?86.7 cm^鈥? for the aug-pc-1-333221 basis set. To further check the performance of the selected basis sets, we evaluate intermolecular bound states of the complexes. The differences between calculated vibrational levels using the CCSD(T)/(Z)Pol-33211 and CCSD(T)/aug-cc-pVTZ-33211 benzene鈥揳rgon potentials are small and for the lowest energy levels do not exceed 0.70 cm^鈥?. Such differences are substantially larger for the CCSD(T)/aug-pc-1-33321 calculated potential. For naphthalene鈥揳rgon, bound state calculations demonstrate that the (Z)Pol-3322 and aug-pc-1-333221 potentials are of similar quality. The results show that these surfaces differ substantially from the available MP2/aug-cc-pVDZ potential. For the anthracene鈥揳rgon complex it proved advantageous to calculate interaction energies by using the (Z)Pol and the aug-pc-1 basis sets, and we expect it to be increasingly so for complexes containing larger aromatic molecules.