Spectroscopic characterization of the X 1Σ+0 and C 1Π1 states of the ZnKr molecule

Wallace, Ingvar; Ryter, Jarral; Breckenridge, W. H.
January 1992
Journal of Chemical Physics;1/1/1992, Vol. 96 Issue 1, p136
Academic Journal
The X 1Σ+0 and C 1Π1 electronic states of the ZnKr van der Waals molecule have been characterized by laser-induced fluorescence spectroscopy. Spectroscopic constants, bond lengths, and dissociation energies are reported for both states. The substantial amount of data now available on M·RG ‘‘pure-π’’ excited states, where M=Zn, Cd, and Hg and RG=Ne, Ar, Kr, and Xe is also examined critically. It is proposed that the much larger dissociation energies and shorter bond lengths of the pure-π states compared to the ground states is due primarily to the fact that the RG atom, approaching in the nodal plane of the diffuse M(np) orbital, feels an effective positive charge when near the contracted M(ns) ‘‘core.’’ In the cases where re and De have both been determined, effective core charges are calculated to be 0.85–1.00 using a simple model potential with only a ‘‘core-ion/induced-dipole’’ attractive term. Fundamental vibrational frequencies calculated with the same potential also agree well with values determined experimentally for the pure-π states. Detailed comparisons of the properties of the pure-π states of Na·RG vs those of Zn·RG, Cd·RG, and Hg·RG molecules indicate that in the latter cases, the interaction also involves ‘‘back polarization’’ of the M(ns) core electron away from the approaching RG atom, which increases the apparent M(ns) charge.


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