Stereodynamic Imaging of Bromine Atomic Photofragments Eliminated from 1-Bromo-2-methylbutane Oriented via Hexapole State Selector

Both single-laser and two-laser experiments were conducted to look into the ion-imaging of Br*(P-2(1/2)) and Br(P-2(3/2)) photofragmented from 1-bromo-2-methylbutane in the range 232-240 nm via a detection scheme of (2+1) resonance-enhanced multiphoton ionization. The angular analysis of these photofragment distributions yields the anisotropy parameter beta = 1.88 +/- 0.06 for the Br* excited state which arises from a parallel transition, while beta = 0.63 +/- 0.09 for the Br ground state indicates the contribution from both a perpendicular transition and a non-adiabatic transition. When a hexapole coupled with an orienting field was implemented, the parent molecules are spatially oriented to yield an orientation efficiency vertical bar cos theta | of 0.15. Besides the chi angle between the recoil velocity v and the transition dipole moment mu, orienting molecules allows for the evaluation of the angle a between v and the permanent molecular dipole moment d. The angular analysis of Br* photofragment distribution yields chi = 11.5 degrees and alpha in the range from 160 degrees to 180 degrees with weak dependency. In the two-laser experiments, the angular anisotropy of Br photofragment distribution was found to be smaller (0.38 +/- 0.10) when the photolysis wavelength was red-shifted to 240 nm, suggesting the increasing contributions from perpendicular transitions.