A. Geers et al., ROTATION-VIBRATION STATE-RESOLVED UNIMOLECULAR DYNAMICS OF HIGHLY EXCITED CH3O((X)OVER-TILDE(2)E) .2. INTRAMOLECULAR VIBRATIONAL DYNAMICS OF EXCITED C-O STRETCH STATES, The Journal of chemical physics, 101(5), 1994, pp. 3634-3648
The stimulated emission pumping (SEP) spectra of highly excited CH3O (
X (2)E) reported in the preceding paper [A. Geers, J. Kappert, F Temps
, and J. Wiebrecht, J. Chem. Phys. 101, 3618 (1994); paper I] are anal
yzed to extract quantitative data on the collision-free intramolecular
vibrational dynamics of the molecules. Attention is focused on the sp
ectra and dynamics of the excited C-O stretch vibration (nu 3) states
at energies between 3 000 cm(-1)less than or equal to E less than or e
qual to 10 000 cm(-1). The spectra are found to exhibit a rather sudde
n transition at E approximate to 5000 cm(-1) from the regular, assigna
ble properties at low energies to the ''statistical'' region at high e
nergies. This IVR ''threshold'' is approximately 2000 cm(-1) below the
asymptotic H-H2CO dissociation limit of the molecule. The observed de
nsities of states at these energies approach the full J- and symmetry-
sorted rovibronic densities estimated from harmonic state counts. The
nearest-neighbor level spacing distribution in the spectra and the mag
nitude of the inferred root mean square level coupling matrix elements
support the assumption of nearly ''ergodic'' molecular properties in
this region. From computed time autocorrelation functions, the IVR lif
etimes of the highly excited C-O stretch states are found to be of the
order of tau approximate to 0.2-0.3 ps (nu(3)=5 to 6) Evidence is obt
ained from some spectra for two-tier IVR processes with characteristic
time scales of 0.2 and 2 ps, respectively. The highest excited C-O st
retch states at energies above approximate to 8000 cm(-1) (nu(3) great
er than or equal to 8) appear to be coupled only weakly to neighboring
background states. This last observation hints at the existence of qu
asistable periodic orbits, which are embedded in the quasicontinuum of
dissociative states at these energies.