Short-Range Characterization of the MeAr (Me=Zn, Cd) Ground-State Potentials from Fluorescence Spectra

First-time observed D1(¹Π)_v′=10→X0⁺(¹Σ) fluorescence in ZnAr, and A0⁺(³Π)_v′=4→X0⁺ and D1(¹Π)_v′=7,8→X0⁺ fluorescence in CdAr van der Waals (vdW) molecules were produced in a continuous supersonic molecular beam crossed with a pulsed dye-laser beam, following excitation of single vibronic levels. The dispersed fluorescence spectra displayed characteristic Condon internal diffraction (CID) patterns consisting of bound-free, reflection type, continuous spectra, and, in certain cases, bound-bound discrete features. An analysis of the A0⁺→X0⁺ and D1→X0⁺ bound-bound spectra indicates that Morse functions are adequate representations of the X0⁺ potential energy (PE) curves below their dissociation limits. In simulation of the A0⁺→X0⁺ and D1→X0⁺ bound-free spectra, the Morse, Lennard-Jones L-J(n−6), and Maitland-Smith M-S(n₀,n₁) functions were tested, and the respective M-S(11.3, 9.0) and M-S(10.6, 7.0) potentials were found to be good representations for the repulsive walls of the X0⁺ PE curves of ZnAr and CdAr, respectively, over the short range, R=2.45-4.38 Å (ZnAr) and R=2.85-4.31 Å (CdAr), of internuclear separations.