Photofragmentation of M-State Polarized Molecules: Comparison of Quantum and Semiclassical Treatments

Abstract

A beam of rovibrational energy level selected and magnetic state polarized (X)1A1) CD3I |JKM〉 ≡ |111〉 was photodissociated at 266 nm. State-selective detection of the photoproducts allowed determination of elements of the transition dipole matrix or T matrix. We present here the methodology involved in the extraction of the T matrix elements from such quantum state-to-quantum state experiments and furthermore compare the results to cases where quantum and semiclassical descriptions are expected to be most accurate. A brief description of the effects of nuclear-spin depolarization on the accurate determination of the T matrix elements is also included. After depolarization is taken into account, the magnitudes of the T matrix elements for the R(ΔJ = 1) and Q(ΔJ = 0) product waves were 6.4 and 6.9, respectively. The relative phase between these waves was ±11°, which is due purely to the structure of the excited state potential surface. These T matrix values give a β = 1.94 for the photodissociation of CD3I...