Bond‐dissociation energies of cations—Pushing the limits to quantum state resolution

Currently available concepts for measuring the bond-dissociation energy of cations D(o) are reviewed. Starting from the traditional approach of directly measuring the threshold energy for the appearance of fragment ions, attention is directed towards indirect measurements, where threshold energies are obtained by extrapolation of, for example, rate constants k(E) or kinetic energy release (KER) data to the threshold of interest. More recent high precision techniques again utilize direct measurements, for example, of the disappearance energy of the parent ion. Most precise data are obtained from quantum state resolved measurements of the dissociation energy, where the threshold energy is bracketed by the existing quantum states above and below the threshold. Ultimately the limits can even be pushed beyond the bracketing limit, by investigating steps on the lineshape of homogeneously broadened single rotational transitions.