Accession Number : ADA139101

Title :   Dispersion Spectroscopy of Optical Electron Transfer in Solution.

Descriptive Note : Technical rept.,

Corporate Author : NEW YORK UNIV NY DEPT OF CHEMISTRY

Personal Author(s) : Delahay,P. ; Dziedzic,A.

Report Date : FEB 1984

Pagination or Media Count : 36

Abstract : The effect of dielectric dispersion of the solvent on optical electron transfer is interpreted as a shift delta G sub d of the free energy level of the ground state in the photoionization process. The shift delta G sub d is derived for transparent and absorbing solvents by application of the Marcus theory of nonequilibrium polarization of a continuous medium. Only the inner-sphere solvation shell contributes significantly to the dispersion correction delta G sub d. Application is made to photoelectric emission by solutions. The effect of dispersion on the energetics of emission causes deviation from the expected emission law. The resulting dispersion spectra are obtained for photoelectron emission by 17 inorganic anions in aqueous solution in the 7 to 10 eV range of photon energies. The spectra primarily result from dispersion of the solvent and are not strongly affected by the nature of the photoionized anion. Experimental dispersion spectra agree well with the theoretical spectrum predicted from the real and imaginary dielectric constants obtained from reflectance spectroscopy data of liquid water. Dispersion spectroscopy of optical electron transfer developed in this work provides an experimental probe of the inner-sphere solvation shell. (Author)

Descriptors :   *Spectroscopy, *Dielectric properties, *Electron transfer, *Photoelectrons, Dispersing, Solvents, Shifting, Energy levels, Free energy, Ground state, Photoionization, Photoelectric emission, Solvents, Polarization, Emission spectra, Solvation

Subject Categories : Electricity and Magnetism
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE