Solvent and temperature effects in the photoionization of tetramethyl-p-phenylenediamine

Holroyd, Richard A.; Russell, Robert L.

doi:10.1021/j100614a013

Cited by 158 publications

(41 citation statements)

References 10 publications

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“…The increase in V 0 , as shown elsewhere, 86 can be rationalized using the model of Springett, Jortner, and Rice 46 in its formulation by Kevan et al 87 This is illustrated in Fig. 5(c) using the experimental data for n-hexane 86 and calculated V 0 energies for methylcyclohexane. Following the decrease in E t with the increasing temperature, the activation energy for µ e should also decrease.…”

mentioning

confidence: 68%

Photostimulated electron detrapping and the two-state model for electron transport in nonpolar liquids

Shkrob¹,

Sauer²

2005

The Journal of Chemical Physics

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In common nonpolar liquids, such as saturated hydrocarbons, there is a dynamic equilibrium between trapped (localized) and quasifree (extended) states of the excess electron (the two-state model). Using time-resolved dc conductivity, the effect of 1064 nm laser photoexcitation of trapped electrons on the charge transport has been observed in liquid n-hexane and methylcyclohexane. The light promotes the electron from the trap into the conduction band of the liquid. From the analysis of the two-pulse, two-color photoconductivity data, the residence time of the electrons in traps has been estimated as ca. 8.3 ps for n-hexane and ca. 13 ps for methylcyclohexane (at 295 K). The rate of detrapping decreases at lower temperature with an activation energy of ca. 200 meV (280-320 K); the lifetime-mobility product for quasifree electrons scales linearly with the temperature. We suggest that the properties of trapped electrons in hydrocarbon liquids can be well accounted for using the simple spherical cavity model. The estimated localization time of the quasifree electron is 20-50 fs; both time estimates are in agreement with the "quasiballistic" model. This localization time is significantly lower than the value of 310±100 fs obtained using time-domain terahertz (THz) spectroscopy 2.for the same system [E. Knoesel et al., J. Chem. Phys. 121, 394 (2004)]. We suggest that the THz signal originates from the oscillations of electron bubbles rather than the freeelectron plasma; vibrations of these bubbles may be responsible for the deviations from the Drude behavior observed below 0.4 THz. Various implications of these results are discussed.

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mentioning

confidence: 68%

Photostimulated electron detrapping and the two-state model for electron transport in nonpolar liquids

Shkrob¹,

Sauer²

2005

The Journal of Chemical Physics

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“…electron mobilities and V, values in TMP and DMB lie between those in the type I hydrocarbons and those in the type 11 hydrocarbons (24)(25)(26)(27)(28)(29)(30)(31)(32)(33). Therefore, we are tempted to say that the absence of electron transfer from the TMP-DMB region into alcohol clusters implies that electrons are not localized in TMP-DMB glasses.…”

Section: Yields Of Trapped Electrorls In Alcohol Clustersmentioning

confidence: 94%

Electron trapping in alcohol clusters in γ-irradiated alcohol-2,2,4-trimethylpentane- 2,2-dimethylbutane glasses at 77 K

Kimura¹,

Yasuda²,

Fukuda³

et al. 1983

Can. J. Chem.

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An optical absorption study has been made on electrons [Formula: see text] trapped in alcohol clusters in γ-irradiated 1-propanol (PrOH) – 2,2,4-trimethylpentane (TMP) – 2,2-dimethylbutane (DMB), 1-butanol (BuOH) – TMP – DMB, and 1-pentanol (PnOH) –– TMP – DMB mixture glasses at 77 K. Hitherto electron transfer from the hydrocarbon region into alcohol clusters has been known to be a major process for [Formula: see text] formation in γ-irradiated alcohol–hydrocarbon glasses. However, in the present systems of PrOH–TMP–DMB, BuOH–TMP–DMB, and PnOH–TMP–DMB, this type of electron transfer was not observed and the [Formula: see text] formation was found to result only from the direct radiolysis of alcohols. In the alcohol concentration range lower than 0.2 electron fraction the yields of [Formula: see text] are less than those expected from the direct radiolysis of alcohols. The average number of alcohol molecules in a cluster in these systems is estimated to be four in the lower alcohol concentration range studied. The position of the absorption maxima for [Formula: see text] in these systems is constant within experimental uncertainties independent of alchohol concentration, which is consistent with the results of a semicontinuum model calculation.

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“…n-hexane (+ 0.04 to + 0.09 eV [6][7][8]) and the adiabatic IP o of pyrene (7.44 eV [ 14]), P + in n-hexane is estimated to be about 1.6 eV according to Equation (1). Holroyd et al reported the adiabatic threshold energy for one-photon ionization of pyrene in 2,2-dimethylpropane (V o -0.43 eV [6]) to be 6.20 eV [-1].…”

Section: Figurementioning

confidence: 99%

“…P / is negative and of the order of 1-2 eV, depending mainly on molecular size of the cation and the dielectric constant of the solvent [5]. V o ranges from 0.6 to + 0.1 eV for saturated hydrocarbon solvent, depending on the solvent [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Two‐Color Two‐Photon Ionization Spectrum of Pyrene in N‐Hexane

1997

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The photoionization process of pyrene in non-polar solvent has been investigated using a two-color two-photon ionization technique. The ionization spectrum near threshold of pyrene in n-hexane was measured by a delayed irradiation of a dye laser 20 ns after an N laser at total excitation energies of 5.9-6.22 eV. The two-photon ionization threshold of pyrene was in the vicinity of 5.9 eV which is larger by 0.7 eV than that expected from the onset of one-photon ionization. The ionization spectrum shows maxima at 5.92 and 5.99 eV which may be assigned to an autoionization process.

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Solvent and temperature effects in the photoionization of tetramethyl-p-phenylenediamine

Cited by 158 publications

References 10 publications

Photostimulated electron detrapping and the two-state model for electron transport in nonpolar liquids

Photostimulated electron detrapping and the two-state model for electron transport in nonpolar liquids

Electron trapping in alcohol clusters in γ-irradiated alcohol-2,2,4-trimethylpentane- 2,2-dimethylbutane glasses at 77 K

Two‐Color Two‐Photon Ionization Spectrum of Pyrene in N‐Hexane

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