Photodissociation and continuum resonance Raman cross sections and general Franck--Condon intensities from S -matrix Kohn scattering calculations with application to the photoelectron spectrum of H sub 2 F sup minus + h. nu. r arrow H sub 2 +F, HF+H + e sup minus
- Department of Chemistry, University of California, Berkeley, CA (US) Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (US)
It is shown how the {ital S}-matrix version of the Kohn variational method for quantum scattering can be readily adapted to compute matrix elements involving the scattering wave function and also matrix elements of the scattering Green's function. The former of these quantities is what is involved in computing photodissociation cross sections, photodetachment intensities from a bound negative ion to a neutral scattering state, or the intensity of any Franck--Condon transition from a bound state to a scattering state. The latter quantity (i.e., a matrix element of the scattering Green's function between two bound states) gives the resonance Raman cross section for the case that the intermediate state in the Raman process is a scattering state. Once the basic {ital S}-matrix Kohn scattering calculation has been performed, it is shown that little additional effort is required to determine these quantities. Application of this methodology is made to determine the electron energy distribution for photodetachment of H{sub 2}F{sup {minus}} to F+H{sub 2}, HF+H. Resonance structure in the {ital J}=0 reaction probabilities is seen to appear in the electron energy distribution.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6934994
- Journal Information:
- Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 92:3; ISSN JCPSA; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Assignment of peaks in photodetachment spectra using predicted densities of reactive states: Application to H sub 2 F sup minus and D sub 2 F sup minus
Probing the dynamics on the Franck-Condon region and exit channel regions of dissociating H{sub 2}S: Resonance Raman spectra at excitation wavelengths from 199-203 NM
Related Subjects
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTIONS
CROSS SECTIONS
DECOMPOSITION
DISSOCIATION
ELECTRON DETACHMENT
ELECTRON SPECTROSCOPY
FRANCK-CONDON PRINCIPLE
HYDROFLUORIC ACID
HYDROGEN COMPOUNDS
INELASTIC SCATTERING
INORGANIC ACIDS
LIGHT SCATTERING
MATRICES
PHOTOCHEMICAL REACTIONS
PHOTOELECTRON SPECTROSCOPY
PHOTOLYSIS
RAMAN SPECTRA
RESONANCE SCATTERING
S MATRIX
SCATTERING
SPECTRA
SPECTROSCOPY
VARIATIONAL METHODS