Reversible hole trapping in liquid cyclohexane

Article Abstract:

The first direct evidence of reversible trapping of solvent holes in saturated hydrocarbons is reported. 1,1- and trans-1,2-dimethylcyclopentanes, methylcyclohexane, and 2,3-dimethylpentane are shallow traps for solvent holes in liquid cyclohexane. The reversible trapping occurs via charge transfer, but the difference in the ionization potentials (IP) deltaIP(sub liq) of the solvent and the solute and the driving force deltaG(super o) of the scavenging reaction do not correlate with the rate constants of this charge transfer. It is proposed that these rate constants are controlled by the height of the activation barrier that can be estimated from the difference in the vertical IP for the solute and adiabatic IP of the solvent.

Cyclohexane

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Hole injection and formation of polarons in cycloalkane liquids

Article Abstract:

Rapidly hopping solvent holes are formed following ionization of the solvent or photoexcitation of a solute radical cation. In Decalins and methylcyclohexane, hopping is thermally activated with activation energies of the same order as the energy of solvent reorganization. The opposite seems true for cyclohexane, as the hopping does not appear to be thermally activated. These were gleaned from an investigation of the temperature dependence of scavenging rate constants and conductivity signals for the solvent holes in liquid cyclohexane, methylcyclohexane and Decalins.

Polarons

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Photophysics of hole injection in liquid cycloalkanes

Article Abstract:

A study was conducted to show that the hole injection is the major photoreaction of aromatic radical cations in cycloalkanes and report a number of quantum yields in trans-decalin. The use of laser-induced dc conductivity to detect minute concentrations of aromatic radical cations against the background of other ions and neutral excited states was examined. Results showed that the scavenging of solvent holes in cycloalaknes occurs through the formation of a shirt-lived collision complex.

Ions, Cations, Alkanes

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