Lc. Pipes et al., PHOTOFRAGMENTATION OF M-STATE POLARIZED MOLECULES - COMPARISON OF QUANTUM AND SEMICLASSICAL TREATMENTS, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(41), 1997, pp. 7600-7604
A beam of rovibrational energy level selected and magnetic state polar
ized ((X) over tilde)(1)A(1)) CD3I \JKM] = \111] was photodissociated
at 266 nm. State-selective detection of the photoproducts allowed dete
rmination of elements of the transition dipole matrix or T matrix. We
present here the methodology involved in the extraction of the T matri
x elements from such quantum state-to-quantum state experiments and fu
rthermore 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 determinat
ion of the T matrix elements is also included. After depolarization is
taken into account, the magnitudes of the T matrix elements for the R
(Delta J = 1) and Q(Delta J = 0) product waves were 6.4 and 6.9, respe
ctively, The relative phase between these waves was +/-11 degrees, whi
ch is due purely to the structure of the excited state potential surfa
ce, These T matrix values give a beta = 1.94 for the photodissociation
of CD3I at 266 nm.