Abstract

A combined analysis of discrete infrared and microwave spectra, elastic and inelastic differential cross section measurements, and virial coefficient data has been used to determine improved potential energy surfaces for the H2–Ar, –Kr, and –Xe systems. Key improvements over previous surfaces for these species are an improved delineation of the diatom bond length dependence of the potential anisotropy, and the first experimental determination of a distinct P4(cos θ) anisotropy for an atom–diatom system. The effective anisotropy strength seen by bound state properties (such as transition frequencies) is found to increase from H2–Ar to H2–Kr to H2–Xe, although that seen by properties sensitive to the short-range potential (such as rotational predissociation and rotational inelasticity) decreases along this series. This reflects the lack of conformality of the various potentials; however, both these and analogous trends predicted for properties such as vibrational frequency shifts and vibrational inelasticity are readily understood in terms of the detailed properties of these surfaces.

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