Journal of Chemical Physics, Vol.99, No.12, 9472-9481, 1993
Characterization of the 1st Excited (1)Pi(1) and the Ground X (1)Sigma(+) States of Mgxe .1. Analysis of the (1)Pi(-X (1)Pi(+) Bound Bound Transitions
Laser induced fluorescence (LIF) excitation spectra recorded for the vibrational bands in the Mg(3s3p 1P1) . Xe(1PI1) <-- Mg(3s3s 1S0) . Xe(X 1SIGMA+) system have been analyzed, yielding absolute vibrational assignments and values of omega(e)x(e) = 1.585 +/- 0.02 and omega(e) = 97.5 +/- 1.0 cm-1 for the 1PI1 state of (MgXe)-Mg-24-Xe-132. From a Birge-Sponer extrapolation, the well depth of this state is estimated to be 1500 cm 1. Simulations of rotationally structured spectra of three of the most intense vibrational bands are consistent with R(e)" = 4.56 +/- 0.12 angstrom for the X 1SIGMA+ state. From Morse function extrapolation of the excited state rotational constants from the simulations, and Franck-Condon intensity simulations of the 1PI1 <-- X 1SIGMA+ vibrational progressions, R(e)’ for the 1PI1 state is estimated to be 3.07 +/- 0.10 angstrom. The 1PI1 state of MgXe fluoresces strongly. The corresponding 1PI1 states of ZnXe and CdXe do not fluoresce, but "action" spectra from the production (via predissociation) of metal atom P-3(J) states are observed. Possible reasons for these differences are discussed in terms of spin-orbit induced predissociation. It is concluded that predissociation of the MgXe (1PI1) state is not observed because the crossing between the repulsive 3SIGMA1+ and the attractive 1PI1 potential curves does not occur until energies higher than those accessible experimentally. Possible reasons for the behavior of the diatomic MgXe(1PI1) state vs that of Mg(3s3p P-1(1)) isolated in solid Xe, where production of Mg(3s3p P-3(J)) states competes with Mg(3s3p P-1(1)) fluorescence, are also discussed. Finally, the attractive "bonding" interactions in the MgXe(1PI1) state are analyzed in terms of electrostatic interactions and compared with those for other PI-type states of metal/rare-gas van der Waals diatomic molecules.
Keywords:SPECTROSCOPIC CHARACTERIZATION;INTERATOMIC POTENTIALS;VANDERWAALS MOLECULE;LASER SPECTROSCOPY;ELECTRONIC STATES;E3-SIGMA+ STATES;CDAR;HGAR;ATOMS;CDNE