Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases · 1973 · 121 citations · 0 references
Natural SciencesChemistryPhysicsMolecular PhysicsPhysical ChemistrySpectroscopyAlcohol AbsorptionChemical ThermodynamicsSolution ChemistrySolvation EffectsSolvation TheoryMeltingMolecular Relaxation ProcessesRelaxation In LiquidsSolvent Effects On Electronic SpectraSolvent Effects On SpectraTemperature Dependence Of Absorption SpectraTemperature Effects On Electronic SpectraTemperature Effects On Spectra
The spectra due to electrons in alcohols at temperatures near their melting points show absorptions in the far and infra-red which, in general, decay to produce increased absorptions in the visible. At these temperatures the time for these changes increases in the order methanol, ethanol, n-butyl, isopropyl, n-propyl alcohol. For the latter the half-life of the absorption decay is given by τs=A exp E/RT where log10A=–15.7 and E= 25 kJ (5.9 kcal). Addition of solutes which react with electrons decreases the initial infra-red absorption and is interpreted as reaction with electrons before they become solvated. The observations are discussed in terms of molecular relaxation and electron migration.