Small transition metal-containing cations have become attractive candidates for various hydrocarbon catalysis applications. Several metal oxide cation species are known to activate methane and convert it to methanol, with up to 100% selectivity, while metal sulfide cations are known to activate larger hydrocarbons; each reaction involves dissociation of the metal-nonmetal bond. However, most of these ions are open shell systems with many low-lying electronic states, making them difficult to treat theoretically in models of heterogenous catalysts. Imaging the dissociation products of metal-containing ions reveals a wealth of information on how energy is distributed in the bond-dissociation process by measurement of kinetic energy release (KER) upon photolysis. Precise bond dissociation energies (D0) measured from image KER provide useful benchmarks for assessing the accuracy of current functionals in treating metal-containing species. Imaging also characterizes these species’ dissociation dynamics, such as tendencies toward spin allowed and forbidden dissociation pathways, helping to determine the viability of proposed catalytic mechanisms. Results from current imaging studies on NiO+ and NiS+ are presented, along with recently completed work on the simplest group 13 metal dimer system, Al2+.

Photofragment ion imaging: Measuring the bond energetics and dissociation dynamics of diatomic metal cations

256th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.