The H2O2+ potencial energy surfaces dissociating into H+/OH+: Theoretical análisis of the isotopic effects

B. GERVAIS; E. GIGLIO; L. ADOUI; A. CASSIMI; D. DUFLOT; M. GALASSI

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2009 vol. 131 p. 1 - 11

0021-9606

We present a detailed study of the potential energy surfaces of the water dication correlatingasymptotically with O3Pand O1D. Using ab initio multireference configuration interaction method, we computed a large ensemble of data, which was used to generate a fit of each potentialenergy surface for bending angles 80° degrees and OH distances ROH1.0 a.u. The fit is used to investigate the dissociation dynamics along each potential energy surface for several initialgeometries corresponding to Franck Condon transition from neutral or singly ionized watermolecule. For each case, we determine the dissociation channels and we compute the kinetic energyrelease and angular momentum distribution of the final arrangements. Among the eight potentialenergy surfaces investigated here, only the lowest triplet and the three lowest singlet can lead to theformation of bound residual fragment. The dissociation of HOD2+ presents a strong preference for OH rather than OD bond breakage.