Studies of simple chemical reactions in solution: Iodine photodissociation, recombination, and relaxation and the development of autoregressive procedures for application to stochastic simulations

Technical Report · Fri Sep 01 00:00:00 EDT 1989

DOI:https://doi.org/10.2172/5729529· OSTI ID:5729529

Smith, D. E.

Picosecond time-resolved experimental studies of the iodine photodissociation and recombination reaction were performed in order to clarify the early time dynamics of the dissociation and solvent caging processes. Results suggest that predissociation is much more rapid ({le} 1 ps) than previously thought, and also indicate that geminate recombination may be rapid ({le} 2 ps). A simple theoretical model for vibrational relaxation of diatomic molecules in solution, based on the generalized Langevin equation (GLE), was also developed. In this model, the memory function in the GLE is determined directly form equilibrium force autocorrelation functions for the individual atoms of the diatomic dissolved in the solvent of interest. The vibrational relaxation model was tested on the system of iodine in liquid xenon, and through comparison with molecular dynamics simulations was shown to perform very well. Results are discussed in terms of simplifying assumptions that the solvent interaction with the diatomic can be characterized by equilibrium dynamics of single atoms in solution. 117 refs., 17 figs., 3 tabs.

• Research Organization: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: DOE/ER
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5729529
• Report Number(s): LBL-27795; ON: DE90001142
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IODINE
DISSOCIATION
C CODES
CARBON TETRACHLORIDE
CHEMICAL REACTIONS
COMPUTERIZED SIMULATION
GROUND STATES
I CODES
LANGEVIN EQUATION
M CODES
PHOTOCHEMICAL REACTIONS
SOLUTIONS
VIBRATIONAL STATES
CHLORINATED ALIPHATIC HYDROCARBONS
COMPUTER CODES
DISPERSIONS
ELEMENTS
ENERGY LEVELS
EQUATIONS
EXCITED STATES
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
MIXTURES
NONMETALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
SIMULATION
400201* - Chemical & Physicochemical Properties