Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions
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 National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE; USDOD; 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
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
Similar Records
Studies of transition states and radicals by negative ion photodetachment
Studies of transition states and radicals by negative ion photodetachment
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTION KINETICS
PHOTOELECTRON SPECTROSCOPY
MOLECULES
ANGULAR DISTRIBUTION
ANIONS
BROMINE
CHEMICAL REACTIONS
CHLORINE
FLUORINE
HYDRIODIC ACID
HYDROCARBONS
HYDROGEN
QUANTUM MECHANICS
CHARGED PARTICLES
DISTRIBUTION
ELECTRON SPECTROSCOPY
ELEMENTS
HALOGEN COMPOUNDS
HALOGENS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
IODINE COMPOUNDS
IONS
KINETICS
MECHANICS
NONMETALS
ORGANIC COMPOUNDS
REACTION KINETICS
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
664400 - Experimentally Derived Information on Atomic & Molecular Properties- (1992-)