Journal of Physical Chemistry A, Vol.108, No.45, 9945-9956, 2004
Vibrational mode effects as a probe of inter-channel coupling in the reactions of formaldehyde cation with ammonia and water
We report the effects of collision energy (E-col) and five different H2CO+ vibrational modes on reaction of H2CO+ with ND3 and D2O over the center-of-mass E-col range from 0.1 to 2.1 eV. Properties of various complexes and transition states were also examined computationally. For water, the only reaction is proton transfer (PT), going by a direct mechanism over the entire E-col range, with a cross section near the collision limit. H2CO+ vibrational excitation has no effect on reaction with water. Three product channels are observed in reaction with ammonia. Both proton transfer (PT) and charge transfer (CT) have large cross sections over the entire energy range. Hydrogen abstraction by H2CO+ from ammonia (HA) accounts for <2% of the total product signal but is a mechanistically interesting channel. Both PT and HA go by direct mechanisms over most of the E-col range, but complex mediation may be important at the lowest energies. All three channels are mode-specifically affected by H2CO+ vibrational excitation. Vibration controls total reactivity but has essentially no effect on product branching. Charge transfer during reactant approach appears to have a large effect on subsequent PT and HA reactions.