Three-dimensional potential energy surface of the Ar-OH(2Πi) complex

Pure rotational transitions in the ground state for Ar-OH and Ar-OD [Y. Ohshima , J. Chem. Phys. 95, 7001 (1991) and Y. Endo , Faraday Discuss. 97, 341 (1994)], those in the excited states of the OH vibration, nu(s)=1 and 2, observed by Fourier-transform microwave spectroscopy in the present study, rotation-vibration transitions observed by infrared-ultraviolet double-resonance spectroscopy [K. M. Beck , Chem. Phys. Lett. 162, 203 (1989) and R. T. Bonn , J. Chem. Phys. 112, 4942 (2000)], and the P-level structure observed by stimulated emission pumping spectroscopy [M. T. Berry , Chem. Phys. Lett. 178, 301 (1991)] have been simultaneously analyzed to determine the potential energy surface of Ar-OH in the ground state. A Schrodinger equation, considering all the freedom of motions for an atom-diatom system in the Jacobi coordinate, R, theta, and r, was numerically solved to obtain energies of the rovibrational energy levels using the discrete variable representation method. A three-dimensional potential energy surface is determined by a least-squares fitting. In the analysis the potential parameters, obtained by ab initio calculations at the RCCSD(T) level of theory with a set of basis functions of aug-cc-pVTZ and midbond functions, are used as initial values. The determined intermolecular potential energy surface and its dependence on the OH monomer bond length are compared with those of an isovalent radical complex, Ar-SH. (c) 2006 American Institute of Physics.