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

Journal Article · Thu Feb 01 00:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.458063· OSTI ID:6934994

Zhang, J Z.H.; Miller, W H ^[1]

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1. 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), Vol. 92:3; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROFLUORIC ACID
PHOTOLYSIS
CROSS SECTIONS
DISSOCIATION
ELECTRON DETACHMENT
FRANCK-CONDON PRINCIPLE
LIGHT SCATTERING
PHOTOELECTRON SPECTROSCOPY
RAMAN SPECTRA
RESONANCE SCATTERING
S MATRIX
VARIATIONAL METHODS
CHEMICAL REACTIONS
DECOMPOSITION
ELECTRON SPECTROSCOPY
HYDROGEN COMPOUNDS
INELASTIC SCATTERING
INORGANIC ACIDS
MATRICES
PHOTOCHEMICAL REACTIONS
SCATTERING
SPECTRA
SPECTROSCOPY
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory
400201 - Chemical & Physicochemical Properties