Exploring the new three-dimensional ab initio interaction energy surface of the Ar-HF complex: rovibrational calculations for Ar-HF and Ar-DF with vibrationally excited diatoms.
Several features and the performance of the recently published [P. Jankowski and M. Ziolkowski, Mol. Phys. 104, 2293 (2006)] three-dimensional intermolecular potential energy surface for the Ar-HF complex have been investigated. This full-dimensional surface has been obtained using the method of the local expansion of the exact interaction energy surface [P. Jankowski, J. Chem. Phys. 121, 1655 (2004)] in the Taylor series with respect to intramolecular coordinates. The interaction energies have been calculated with the coupled-cluster supermolecular method with single, double, and noniterative triple excitations. The convergence of the interaction energy with respect to the size of the basis set is discussed. The two-dimensional surfaces resulting from averaging of the full-dimensional surface over the intramolecular vibration of HF have been obtained and directly compared to the empirical H6(4,3,2) set of surfaces proposed by Hutson [J. Chem. Phys. 96, 6752 (1992)]. A very good agreement has been observed. The averaged potentials have been used to calculate the rovibrational energy levels of the Ar-HF and Ar-DF complexes and compared to the experimental data. The accuracy of rovibrational calculations achieved with the new surface is much better than with any of the ab initio surfaces available so far. Predictions of the rovibrational energy levels and spectroscopic constants have also been done for Ar-HF with HF in the v=4,5 vibrational states, and for Ar-DF and DF in the v=3,4 states. The full-dimensional surface studied in this paper is the first ab initio surface which is fully compatible with the empirical H6(4,3,2) surface proposed by Hutson.
Jankowski
Piotr
P
Department of Quantum Chemistry, Institute of Chemistry, Nicolaus Copernicus University, Toruń, Poland. teojan@chem.uni.torun.pl