| Nonequilibrium Electronic Polarization of the Solvent in Photoionization |
JUL 85 |
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| Authors:
P. Delahay; A. Dziedzic; NEW YORK UNIV NY DEPT OF CHEMISTRY
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 | The energetics of photoionization in condensed phases includes a significant contribution from nonequilibrium processes arising from dielectric dispersion of the solvent at the prevailing photon energy. The solvent is polarized by the varying electric field caused by the change of the ionic valence as a result of photoionization. This ionic field varies in a time interval determined by the frequency of incident radiation. The following contributions from nonequilibrium processes to ... |
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| Ionization Energies of Liquids from Energy Distribution, Quantum Yield and Second Derivative Curves |
MAR 85 |
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| Authors:
K. P. Cheung; I. Watanabe; A. Dziedzic; K. von Burg; P. Delahay; NEW YORK UNIV NY DEPT OF CHEMISTRY
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| The energies of the lowest ionization band of eight liquids of low vapor pressure are determined from energy distribution curves (EDC), quantum yield spectra (collected electrons per incident photon as a function of photon energy), and second derivative curves (SDC) of retarding potential curves. Threshold energies from EDC's and quantum yield spectra agree if one takes into account a 0.15 eV shift caused by the spectrometer's rather low resolution and ... |
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| Solvation and Dielectric Dispersion in Optical Electron Transfer |
JUL 1984 |
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| Authors:
P. Delahay; A. Dziedzic; NEW YORK UNIV NY DEPT OF CHEMISTRY
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| The effect of dielectric dispersion of the solvent on the energetics of optical electron transfer is determined quantitatively by variations of the free energy of solvation of the species being photoionized. The solvation free energy varies because the solvent polarizability in the inner-sphere region of the photon absorbing species changes with photon energy on account of dispersion. The solvation free energy is computer for a varying polarizability of the solvent ... |
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| Gas-Liquid Correlation of Ionization Energies |
APR 1984 |
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| Authors:
P. Delahay; A. Dziedzic; NEW YORK UNIV NY DEPT OF CHEMISTRY
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| Ionization potentials of ions and molecules are correlated with the threshold energies of their aqueous solutions for photoelectron emission. Inner- and outer-sphere reorganizations are treated, respectively, in terms of a discrete number of dipoles and a continuous medium model. Calculated and experimental threshold energies are compared for halides and hydroxide ions and water. The threshold and reorganization energies of the hydrated electron are calculated from threshold energies of anions and ... |
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| Inner-Sphere Reorganization in Optical Electron Transfer |
MAR 1984 |
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| Authors:
P. Delahay; A. Dziedzic; NEW YORK UNIV NY DEPT OF CHEMISTRY
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| Free energies for photoelectron emission by aqueous solutions of hexaquocations (V2+, Cr2+, Fe2+) - metal complexes (Fe(CN)6 4-, Co (NH3)6 2+) and inorganic anions (OH, C1-, Br-, I-) are calculated from theory and compared with experimental threshold energies. Good agreement is obtained within the estimated error (+ or - 0.2 eV) on emission free energies. The free energy for outer-sphere reorganization is calculated from a continuous medium model. The inner-sphere ... |
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| Dispersion Spectroscopy of Optical Electron Transfer in Solution |
FEB 1984 |
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| Authors:
P. Delahay; A. Dziedzic; NEW YORK UNIV NY DEPT OF CHEMISTRY
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| 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 ... |
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