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Spectroscopy of Ar–SH and Ar–SD. II. Determination of the three-dimensional intermolecular potential-energy surface.
- Source :
- Journal of Chemical Physics; 8/1/2005, Vol. 123 Issue 5, p054325, 11p, 2 Diagrams, 4 Charts, 6 Graphs
- Publication Year :
- 2005
-
Abstract
- All the pure rotational transitions reported in the previous studies [J. Chem. Phys. 113, 10121 (2000); J. Mol. Spectrosc. 222, 22 (2003)] and newly observed rotation-vibration transitions, P=1/2←3/2, for Ar–SH and Ar–SD [J. Chem. Phys. (2005), the preceding paper] have been simultaneously analyzed to determine a new intermolecular potential-energy surface of Ar–SH in the ground state. A Schrödinger equation considering the three-dimensional freedom of motion for an atom-diatom complex in the Jacobi coordinate, R, θ, and r, was numerically solved to obtain energies of the rovibrational levels using the discrete variable representation method. A three-dimensional potential-energy surface is determined by a least-squares fitting with initial values of the parameters for the potential obtained by ab initio calculations at the RCCSD(T)/aug-cc-pVTZ level of theory. The potential well reproduces all the observed data in the microwave and millimeter wave regions with parity doublings and hyperfine splittings. Several low-lying rovibrational energies are calculated using the new potential-energy surface. The dependence of the interaction energy between Ar and SH(<superscript>2</superscript>Π<subscript>i</subscript>) on the bond length of the SH monomer is discussed. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 123
- Issue :
- 5
- Database :
- Complementary Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 17946973
- Full Text :
- https://doi.org/10.1063/1.1943968