Structure and dynamics from polarized parent/product photofragmentation spectroscopy

Abstract

Energy-level selected nitrosyl chloride (ClNO) was rotationally polarized (aligned/oriented) and photodissociated at 355 nm. Polarization sensitive detection of the NO(²Π) product was used to measure the magnitudes and relative phases of the transition amplitudes (T-matrix elements) for the coherent excitation of continuum wavefunctions representing the dissociating molecule on the excited potential energy surface. Rotational state-populations were also measured and a smaller number of ∣NΩ) levels were found to be occupied than in non-state-selected, jet-cooled experiments. The theoretical formalism necessary for the extraction of the T-matrix elements from fully polarized experiments is also presented. Finally, hexapole focusing curves demonstrate excellent ∣JK) energy-level selection for the parent ClNO and the NO(²Π) photofragment angular distribution demonstrates for the first time dipole orientation and rotational alignment, i.e., ∣M∣ selection, of a state-selected asymmetric top by an electrostatic hexapole.