Spin–orbit interaction mediated molecular dissociation

Abstract

The effect of the spin-orbit interaction to photofragmentation is investigated in the mercury(II) bromide (HgBr2) molecule. Changes in the fragmentation between the two spin-orbit components of Hg 5d photoionization, as well as within the molecular-field-splitted levels of these components are observed. Dissociation subsequent to photoionization is studied with synchrotron radiation and photoelectron-photoion coincidence spectroscopy. The experimental results are accompanied by relativistic ab initio analysis of the photoelectron spectrum.

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)

“…Differences in fragmentation can arise if the internal energy is in vibrational rather than electronic form, or if it is in electronic states with different charge distributions 25,26 . Fragmentation differences can also arise from spin-orbit and molecular field splittings, as previously found by the Huttula group 27 . In Auger decay such effects can be seen as the influence of the core hole within its lifetime on the nuclear positions and motion, which affects the dicationic states.…”

Role of ultrafast dissociation in the fragmentation of chlorinated methanes

“…The coincidence logic follows the schemes utilized earlier 17,39,[41][42][43][44][45] , where the electron detection from the HDA sends a signal to the pulsed voltage source (Directed Energy Inc. model PVX-4450) which raises the voltages in the extraction region for a specified time interval, allowing the measurement of the ion flight times. Due to the inherent di↵erences between the transmissions of the HDA and the TOFMS, there exists a high likelyhood of producing false coincidences between electrons and ions that in reality have no correlation.…”