Journal of Physical Chemistry, Vol.98, No.37, 9233-9241, 1994
Geometries and Energy Separations of Electronic States of Gef2, Snf2, and PbF2 and Their Positive-Ions
Seven singlet and triplet electronic states of GeF2, SnF2, and PbF2 and the (2)A(1) and B-2(1) electronic states of GeF2+, SnF2+, and PbF2+ are investigated. We employed complete active space multiconfiguration self-consistent-field followed by multireference singles + doubles configurations interaction which included up to 1.3 million configurations. Complete bending potential energy surfaces of eight singlet and triplet electronic states of GeF2 are obtained. The ground state of MF(2) (M = Ge, Sn, Pb) molecules is the X(1)A(1) state with theta(e) between 92 degrees and 98 degrees while r(e)(M-F) are 1.723, 1.865, and 2.139 Angstrom, respectively. The ground state of MF(2)(+) species is found to be of X(2)A(1) symmetry. The adiabatic ionization potentials are obtained. In addition, spin-orbit effects are included for PbF2 using the relativistic configuration interaction method. Our computed spectroscopic constants of the ground and excited states of GeF2, SnF2, and PbF2 species are in good agreement with both ultraviolet absorption and infrared spectra of these species. The computed bond energies are also in good agreement with the measured values. Several other electronic states are predicted which are yet to be observed.
Keywords:LASER-INDUCED FLUORESCENCE;CONFIGURATION-INTERACTION CALCULATIONS;RELATIVISTIC EFFECTIVE POTENTIALS;SPIN-ORBIT OPERATORS;LOW-LYING STATES;INFRARED-SPECTRA;VIBRATIONAL FREQUENCIES;A1A"-X1A’ TRANSITION;MICROWAVE-SPECTRUM;ABINITIO