Imaging the Atomic Orientation and Alignment in Photodissociation

Frequency modulated circular dichroism spectroscopy: application to ICN photolysis

“…The difference between the co-and counter-rotating profiles, acquired in geometries 3 and 4, is solely due to orientation of the CN fragments, the preference for one sense of rotation over the other. This is clear from the lineshape given in equation (3), where as noted previously the difference between profiles with CP = 0 and 1 is only the h (1) term, dependent on the two orientation moments.…”

“…There are several ways in which those correlations can be parameterised [1,3,5,46]. We choose to use the bipolar moment formalism introduced by Dixon [43].…”

“…(c) P 1 (44) acquired simultaneously in geometries 3 and 4. In (a) and (b), filled circles represent data recorded in geometry (1), while open circles represent data recorded in geometry (2), as shown in figure 1. In (c), open circles represent data recorded in geometry (3), while filled circles represent data recorded in geometry (4).…”

“…The past ten years has seen an explosion of interest in the study of the velocity-resolved angular momentum orientation of photofragments [1,2]. This has been driven by the F o r P e e r R e v i e w O n l y 2 realization that these vector properties contain information not just on the magnitudes of different photofragment pathways, but also on their relative phases [3][4][5].…”

Determination of all scattering phases and amplitudes in the photodissociation of a diatomic molecule

“…In general, multiple electronic states, each described by its own adiabatic potential energy curve, will correlate to two open-shell atomic products, and the route by which the system evolves from a molecular structure to two separated atoms may involve non-adiabatic transitions between these potential curves. A so-called "complete" photodissociation experiment [4] seeks to measure all the non-adiabatic transition probabilities (or, equivalently, the asymptotic amplitude on each potential energy curve correlating to the separated atom limit), and the phases of the nuclear wavefunctions on each adiabatic electronic potential -thus deriving the components of T-matrix elements used to treat the theory of photodissociation [5]. The polarization of the electronic angular momentum of the atoms is described most conveniently…”