Picosecond spectroscopy and solvation clusters. The dynamics of localizing electrons in polar fluids

Journal Article · Thu Jul 08 04:00:00 EDT 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100211a007· OSTI ID:6628517

Kenney-Wallace, G A ^[1]; Jonah, C D

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1. Univ. of Toronto, Ontario

New spectroscopic evidence concerning the dynamics of electron-induced solvation clusters in polar liquids is presented and integrated with previous picosecond data, in order to outline the roles molecular dynamics and structure can play both in initiating electron localization at subpicosecond times and in governing the solvation dynamics to form e/sup -//sub s/ in the picosecond domain. Particulr emphasis is placed on the picosecond time-resolved absorption spectroscopy of electrons in a wide range of alcohols and alcohol-alkane systems at 300/sup 0/K as a framework for the cluster model of electron solvation. While the configurationally relaxed final quantum state of e/sup -//sub s/ appears identical for e/sup -//sub s/ generated by different techniques, it is possible that the time evolution of the solvation cluster and the dynamics of electron populations between localized and continuum states could be influenced by the initial state of the system. Selected examples are discussed for alcohols, amines, and water, and comparisons are made for picosecond observations from different visible and IR spectroscopic techniques, NMR, and complementary nanosecond electron mobility data to demonstrate the overall consistency of a model in which only the dynamical, microscopic properties of the liquid determine these solvation events.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6628517
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:14; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500 -- Photochemistry
400600* -- Radiation Chemistry
ABSORPTION SPECTRA
ALCOHOLS
ALKANES
BEAMS
BUTANOLS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMISTRY
CYCLOALKANES
CYCLOHEXANE
CYCLOHEXANOL
DATA
DECANOLS
ELECTROMAGNETIC RADIATION
ELECTRON BEAMS
ELECTRONS
ELEMENTARY PARTICLES
ETHANOL
EXPERIMENTAL DATA
FERMIONS
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INFRARED SPECTRA
IONIZATION
KINETICS
LASER RADIATION
LEPTON BEAMS
LEPTONS
MAGNETIC RESONANCE
MATHEMATICAL MODELS
MEDIUM TEMPERATURE
METHANOL
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
OCTANOLS
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
OXYGEN COMPOUNDS
PARTICLE BEAMS
PENTANOLS
PHOTOIONIZATION
PROPANOLS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
REACTION KINETICS
RESONANCE
SOLVATED ELECTRONS
SOLVENTS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
WATER