A new potential energy surface for OH(A (2)Sigma(+))-Kr: The van der Waals complex and inelastic scattering

作者：Chadwick H^*; Brouard M; Chang Y P; Eyles C J; Perkins T; Seamons S A; Klos J; Alexander M H; Aoiz F J

来源：Journal of Chemical Physics, 2012, 137(15): 154305.

DOI：10.1063/1.4757859

• ab initio calculations
• atom-molecule collisions
• bound states
• coupled cluster calculations
• excited states
• krypton
• oxygen compounds
• potential energy surfaces
• quantum beat spectra
• quantum theory
• quasimolecules
• rotational states
• vibrational states
• Zeeman effect

New ab initio studies of the OH(A(2)Sigma(+))-Kr system reveal significantly deeper potential energy wells than previously believed, particularly for the linear configuration in which Kr is bound to the oxygen atom side of OH(A(2)Sigma(+)). In spite of this difference with previous work, bound state calculations based on a new RCCSD(T) potential energy surface yield an energy level structure in reasonable accord with previous studies. However, the new calculations suggest the need for a reassignment of the vibrational levels of the electronically excited complex. Quantum mechanical and quasi-classical trajectory scattering calculations are also performed on the new potential energy surface. New experimental measurements of rotational inelastic scattering cross sections are reported, obtained using Zeeman quantum beat spectroscopy. The values of the rotational energy transfer cross sections measured experimentally are in good agreement with those derived from the dynamical calculations on the new adiabatic potential energy surface.