A velocity map imaging study of gold-rare gas complexes: Au-Ar, Au-Kr, and Au-Xe.

The ultraviolet photodissociation dynamics of the gold-rare gas atom van der Waals complexes (Au-RG, RG = Ar, Kr, and Xe) have been studied by velocity map imaging. Photofragmentation of Au-Ar and Au-Kr at several wavelengths permits extrapolation to zero of the total kinetic energy release (TKER) spectra as monitored in the Au((2)P(3/2)(o)[5d(10)6p]) fragment channel, facilitating the determination of ground state dissociation energies of D(0)(")(Au-Ar) = 149+/-13 cm(-1) and D(0)(")(Au-Kr) = 240+/-19 cm(-1), respectively. In the same spectral region, transitions to vibrational levels of an Omega(') = 1/2 state of the Au-Xe complex result in predissociation to the lower Au((2)P(1/2)(o)[5d(10)6p])+Xe((1)S(0)[5p(6)]) fragment channel for which TKER extrapolation yields a value of D(0)(")(Au-Xe) = 636+/-27 cm(-1). Asymmetric line shapes for transitions to the v(') = 14 level of this state indicate coupling to the Au((2)P(3/2)(o)[5d(10)6p])+Xe((1)S(0)[5p(6)]) continuum, which allows us to refine this value to D(0)(")(Au-Xe) = 607+/-5 cm(-1). The dissociation dynamics of this vibrational level have been studied at the level of individual isotopologues by fitting the observed excitation spectra to Fano profiles. These fits reveal a remarkable variation in the predissociation dynamics for different Au-Xe isotopologues. For Au-Ar and Au-Xe, the determined ground state dissociation energies are in good agreement with recent theoretical calculations; the agreement of the Au-Kr value with theory is less satisfactory.