ABSTRACT
The present study reveals the effects of symmetry on how the distribution and flow of energy play out on the decomposition of small halocarbons. Unimolecular decay of the freons CHFCl2 and CF2Cl2 when ionized has been investigated. Mass spectrometric results that encompass isotope effects (peak heights) and energy distribution in the exit channel (peak shapes) are interpreted by computational methods. Non-statistical processes of electronic predissociation and isolated state decay are shown to be directly associated with molecular symmetry.
ABSTRACT
The loss of a Cl atom from metastable CH2Cl2+ in the mass-analyzed ion kinetic energy experiment is characterized by a borderline zero kinetic energy release and large kinetic isotope effects on chlorine and hydrogen. Ab initio calculations are employed to assist the interpretation in terms of a nonadiabatic reaction involving electronic predissociation of the electronically excited state 2A1 and two-dimensional reaction dynamics. Strong curvature in the reaction coordinate leads to a bobsled effect that accounts for the low kinetic energy release. The kinetic isotope effects enter via the predissociation rate and are interpreted in terms of vibrational overlap integrals.
ABSTRACT
The correction term for the precursor ion signal width in determination of kinetic energy release is reviewed, and the correction term is formally derived. The derived correction term differs from the traditionally applied term. An experimental finding substantiates the inaccuracy in the latter. The application of the "T-value" to study kinetic energy release is found preferable to kinetic energy release distributions when the metastable peaks are slim and simple Gaussians. For electronically predissociated systems, a "borderline zero" kinetic energy release can be directly interpreted in reaction dynamics with strong curvature in the reaction coordinate.
