Experimental studies of the dynamics of the bond-forming reactions of CF22+ with H2O using position-sensitive coincidence spectroscopy

Abstract

The dynamics of the product channels forming OCF++H++HF and HCF2++H++O following the collisions of CF22+ with H2O have been investigated with a new position-sensitive coincidence experiment at a center-of-mass collision energy of 5.6 eV. The results show the formation of OCF+ occurs via the formation of a doubly charged collision complex [H2O-CF2]2+ which subsequently undergoes a charge separating dissociation to form H+ and HOCF2+. The HOCF2+ monocation subsequently fragments to form HF+OCF+. The lifetimes of the collision complex and the HOCF2+ ion are at least of the order of their rotational period. The kinetic energy release in this reaction indicates that it involves the ground state of CF22+ and forms the ground electronic states of OCF+ and HF. The mechanism for forming HCF2+ involves the direct and rapid abstraction of a hydride ion from H2O by CF22+. The resulting OH+ ion subsequently fragments to H++O, on a time scale at least comparable with its rotational period.

Electron transfer and bond-forming reactions following collisions of Cl2+ and HCl2+ with CO

“…For SET we do have a general functional form for f(y) derived from angularly resolved scattering experiments. 42,43 For bond-forming reactions, which coincidence experiments indicate often proceed via a long-lived collision complex 1,24,25,[31][32][33][34][35]40 it seems appropriate to assume f(y) results from an isotropic angular distribution. However, analytically deriving an absolute functional form for the number density distribution of the neutral gas across the source region is impractical given the presence of the plates making up the source region which affect the path of the molecules which effuse from the gas needle.…”

“…The vast majority of observed bond-forming reactions of dications produce a pair of singly charged cations, sometimes accompanied by additional neutral species. 1,10,19,[23][24][25][26][27][28][29][30][31][32][33][34][35] However, a further class of dication reactions has now emerged whereby the formation of a new bond does not bring about separation of the dipositive charge: 36…”

Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

“…_ 1 4 ) T D $ F I G ] [ ( F i g . _ 1 6 ) T D $ F I G ] One of the first bond-forming reactions studied by the PSCO technique was the reaction between CF 2þ 2 and H 2 O [47]. Theoretical calculation of the stationary points on the potential energy hypersurface indicated an analogous shape of the surface as for the reaction CO þ 2 þ D 2 (Fig.…”

“…These results could be interpreted only if the collision complex decomposed to form H + and (HO-CF 2 ) + and this ion subsequently dissociated to HF and OCF + . A slight asymmetry in the scattering of H + scattering with respect to OCF + could be accounted for if the dissociation of (HO-CF 2 ) + occurred within the field of the departing H + [47].…”

Bond-forming and electron-transfer reactivity between Ar2+ and N2

“…The relative intensity for this channel is high (4.3%) compared with typical bond forming dicationneutral reactions, showing an affinity to form the Ar-N bond. [41][42][43][102][103][104][105][106][107] Dissociative double electron transfer Rxn. IV from the Ar 2+ /N 2 collison system results in the formation of N + + N + and has relative intensity of 10.8%.…”