Probing dynamics in the Franck--Condon and exit channel regions of dissociating H[sub 2]S: Emission spectra upon tunable excitation from 199--203 nm
- The James Franck Institute and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)
- Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
This emission, into local mode eigenstates such as 00[sup +]1, 11[sup +]0, 11[sup +]1, 21[sup +]0, 21[sup +]1, evidences the antisymmetric dissociative motion and bending induced near the conical intersection, and dominates the spectrum at excitation wavelengths only near 200 nm. We analyze the excitation wavelength dependence of these features and also of the [ital n]0[sup +]0 progression for [ital n][ge]4, which reflect the exit channel dynamics. The excitation wavelength dependence shows that while the emission spectra do not reveal any dynamics unique to scattering states that access a symmetric stretch resonance in the Franck--Condon region, they do reveal the energy location of and the dynamics at the conical intersection. A reanalysis of other workers' measurements of the SH product vibrational state distribution shows that [ital v]=0 products are strongly favored at excitation wavelengths near the conical intersection.
- DOE Contract Number:
- FG02-92ER14305; W-31109-ENG-38
- OSTI ID:
- 6972096
- Journal Information:
- Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 101:7; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
74 ATOMIC AND MOLECULAR PHYSICS
CHALCOGENIDES
ELECTROMAGNETIC RADIATION
EMISSION SPECTRA
ENERGY-LEVEL TRANSITIONS
EXCITATION
FRANCK-CONDON PRINCIPLE
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
RADIATIONS
SPECTRA
SULFIDES
SULFUR COMPOUNDS
TUNING
ULTRAVIOLET RADIATION