Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions
- Univ. of California, Berkeley, CA (United States)
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-, NCO- and NCS-. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH30H,F + C2H5OH,F + OH and F + H2. A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O(3P, 1D) + HF and F + H2. 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 + H2 system, comparisons with three-dimensional quantum calculations are made.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE; Department of Defense (DOD)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 10131730
- Report Number(s):
- LBL-33328; ON: DE93007669; CNN: AFOSR-91-0084
- Resource Relation:
- Other Information: TH: Thesis (Ph.D.); PBD: Nov 1992
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
MOLECULES
CHEMICAL REACTION KINETICS
PHOTOELECTRON SPECTROSCOPY
ANIONS
CHEMICAL REACTIONS
QUANTUM MECHANICS
ANGULAR DISTRIBUTION
BROMINE
HYDRIODIC ACID
FLUORINE
CHLORINE
HYDROCARBONS
HYDROGEN
400201
400102
664400
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES
CHEMICAL AND SPECTRAL PROCEDURES
EXPERIMENTALLY DERIVED INFORMATION ON ATOMIC AND MOLECULAR PROPERTIES