Journal of Chemical Physics, Vol.103, No.23, 9989-10000, 1995
Charge-Transfer Dynamics in Ion-Polyatomic Molecule Collisions - X(+)+h2O (X=n,Kr) Luminescence Study
H2O+ (A) over tilde (2)A(1)-(X) over tilde B-2(1) luminescence spectra are presented for the X(+)+H2O (X=N,Kr) charge-transfer systems at collision energies ranging between 0.4 and 130 eV (c.m.). The luminescence is attributed to bending vibrational states near-resonant with N+(P-3)+H2O and Kr+(P-2(1/2))+H2O reactants, in agreement with energy resonance and Franck-Condon predictions. H2O+ (A) over tilde-state product vibrational distributions are obtained from spectral simulations. The energy dependence of vibrational state-to-state cross sections is determined for the N+(P-3)+H2O charge-transfer system, where the integral charge-transfer cross section is known. The cross sections are related to semiclassical charge-transfer models. Exothermic product states are interpreted to be primarily governed by curve crossings along the bending coordinate of H2O, while endothermic levels can be rationalized using a Demkov-type mechanism. The Kr+(P-2(1/2))+H2O luminescence study, for which state-selected cross sections are not available, provides product state distributions consistent with this interpretation. The higher optical resolution in that experiment, however, enables a K-substate resolved analysis, as well as an approximate assessment of the product rotational temperature. The observed rotational temperatures are near thermal, implying long-range processes governed by large impact parameters.
Keywords:POTENTIAL-ENERGY SURFACES;ORBITAL ANGULAR-MOMENTUM;SUPRATHERMAL ENERGIES;ELECTRONIC-TRANSITIONS;A2A1-X2B1 TRANSITIONS;TRIATOMIC-MOLECULES;CHEMICAL-REACTIONS;TESICO TECHNIQUE;CROSS-SECTIONS;STATE