PHOTOFRAGMENTATION OF M-STATE POLARIZED MOLECULES - COMPARISON OF QUANTUM AND SEMICLASSICAL TREATMENTS

Citation
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
Citations number
39
Categorie Soggetti
Chemistry Physical
ISSN journal
10895639
Volume
101
Issue
41
Year of publication
1997
Pages
7600 - 7604
Database
ISI
SICI code
1089-5639(1997)101:41<7600:POMPM->2.0.ZU;2-E
Abstract
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.