# The study of basis sets for the calculation of the structure and dynamics of the benzene-Kr complex

## Abstract

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowed us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.

- Authors:

- Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland)

- Publication Date:

- OSTI Identifier:
- 22415861

- Resource Type:
- Journal Article

- Journal Name:
- Journal of Chemical Physics

- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 20; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BENZENE; COMPARATIVE EVALUATIONS; DIPOLE MOMENTS; ENERGY LEVELS; EQUILIBRIUM; EXCITATION; KRYPTON; KRYPTON COMPLEXES; MICROWAVE SPECTRA; MONOMERS; POTENTIAL ENERGY; POTENTIALS; SURFACES; VAN DER WAALS FORCES; YIELDS

### Citation Formats

```
Shirkov, Leonid, and Makarewicz, Jan, E-mail: jama@amu.edu.pl.
```*The study of basis sets for the calculation of the structure and dynamics of the benzene-Kr complex*. United States: N. p., 2015.
Web. doi:10.1063/1.4921566.

```
Shirkov, Leonid, & Makarewicz, Jan, E-mail: jama@amu.edu.pl.
```*The study of basis sets for the calculation of the structure and dynamics of the benzene-Kr complex*. United States. doi:10.1063/1.4921566.

```
Shirkov, Leonid, and Makarewicz, Jan, E-mail: jama@amu.edu.pl. Thu .
"The study of basis sets for the calculation of the structure and dynamics of the benzene-Kr complex". United States. doi:10.1063/1.4921566.
```

```
@article{osti_22415861,
```

title = {The study of basis sets for the calculation of the structure and dynamics of the benzene-Kr complex},

author = {Shirkov, Leonid and Makarewicz, Jan, E-mail: jama@amu.edu.pl},

abstractNote = {An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowed us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.},

doi = {10.1063/1.4921566},

journal = {Journal of Chemical Physics},

issn = {0021-9606},

number = 20,

volume = 142,

place = {United States},

year = {2015},

month = {5}

}