Excitation spectra for the photoassociation of Kr-F and Xe-I collision pairs in the ultraviolet (208-258 nm)

Photoassociation, the bound←free absorption of a photon by a colliding pair of atoms, has been studied experimentally in the Kr-F and Xe-I systems and is demonstrated to be an effective tool for deducing molecular interaction potentials and for determining the dependence of the relative electronic transition moment on internuclear separation (R) in small molecules having dissociative ground states. Specifically, the excitation (``action'') spectrum for the photoassociation of thermalized Kr(4p^{6 1}S₀)-F(2p^{5 2}P) collision pairs, measured at 300 K in the 208-250 nm wavelength region, reveals deeply modulated Franck-Condon structure associated with transitions of Kr-F pairs from the ground state's thermal and vibrational continua to the lowest 27 bound vibrational states (v'=0-26) of the KrF(B ²Σ) excited state. Under these conditions, photoassociation occurs in a narrow (ΔR=0.7-0.8 Å) Franck-Condon region in which the difference potential is a single valued function of R. Similar spectra have been observed for Xe(¹S₀)-I(²P) pairs in the 208-258 nm spectral region that arise from bound←free transitions to the lowest ∼40 vibrational levels of the XeI(B) state. Since the Kr-F and Xe-I collision pairs are photoexcited from the vibrational continuum of the ground state, the atomic pair energy distribution is thermalized and the envelope of the excitation spectrum can be interpreted directly in terms of the relative B-X transition moment, μ(R). Consequently, the behavior of μ(R) has been determined over a limited range in R and, for XeI, μ is found to fall by a factor of 2 in the ∼0.4 Å region extending from R-R_eB≊0.25-0.62 Å. The XeI ground state (X ²Σ_1/2⁺) potential in the 3.0≤R≤5.0 Å interval, derived from photoassociation spectra, is similar to that deduced from scattering experiments. Excited and ground state structural constants derived from numerical quantum simulations of the experimental spectra are presented.