Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

Technical Report · Sun Nov 01 04:00:00 EST 1992

DOI:https://doi.org/10.2172/6716986· OSTI ID:6716986

Bradforth, S E

The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus]], NCO[sup [minus]] and NCS[sup [minus]]. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH[sub 3]0H,F + C[sub 2]H[sub 5]OH,F + OH and F + H[sub 2]. A time dependent framework for the simulation and interpretation of the bound [yields] free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH [yields] O([sup 3]P, [sup 1]D) + HF and F + H[sub 2]. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H[sub 2] system, comparisons with three-dimensional quantum calculations are made.

• Research Organization: Lawrence Berkeley Lab., CA (United States)
• Sponsoring Organization: DOE; DOD; USDOE, Washington, DC (United States); Department of Defense, Washington, DC (United States)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6716986
• Report Number(s): LBL-33328; ON: DE93007669; CNN: AFOSR-91-0084
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
664400 -- Experimentally Derived Information on Atomic & Molecular Properties-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ANGULAR DISTRIBUTION
ANIONS
BROMINE
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE
DISTRIBUTION
ELECTRON SPECTROSCOPY
ELEMENTS
FLUORINE
HALOGEN COMPOUNDS
HALOGENS
HYDRIODIC ACID
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
INORGANIC ACIDS
IODINE COMPOUNDS
IONS
KINETICS
MECHANICS
MOLECULES
NONMETALS
ORGANIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
QUANTUM MECHANICS
REACTION KINETICS
SPECTROSCOPY