Excess electrons in liquid and glassy alkanes produced by pulse radiolysis

Atherton, Stephen J.; Baxendale, J. H.; Busi, F.; Kovács, A.

doi:10.1016/1359-0197(86)90125-6

Cited by 6 publications

(19 citation statements)

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“…The greater problem with these previous measurements is that the cross sections σ for the electron photodetachment were estimated from the spectra of radiolytically generated electrons in room-temperature n-hexane and methylcyclohexane (assuming unity quantum yield for the bound-to-continuum transition). A subsequent study by Atherton et al 42 indicated that the absorptivity of the electron in methylcyclohexane at 1 µm increases as the temperature decreases, and this…”

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confidence: 99%

“…To our knowledge, these are the only data in the literature that are taken across a sufficiently wide range of wavelengths and temperatures. In Figure 5, the normalized spectra obtained by Atherton et al 42 are fitted using the electron bubble model 9,44 assuming, following the previous discussion, that the bubble radii a are not temperature The increase in the U with the decreasing temperature is easy to rationalize, as V 0 rapidly increases in denser medium, whereas the polarization energy changes much less (this trend continues in solid methylcyclohexane, as suggested by the data of McGrane and Lipsky 44 for 77 K shown in Fig. 5(c)).…”

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confidence: 99%

“…Following the decrease in E t with the increasing temperature, the activation energy for µ e should also decrease. The only data for the electron mobility across a temperature interval of comparable width to that explored by Atherton et al 42 are for 3-methylpentane. 57 As the temperature decreases below 200 K, the electron mobility becomes lower than 10 -10 cm 2 /Vs and the activation energy increases from 140 meV to 400 meV.…”

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confidence: 99%

“…Atherton et al 42 obtained a series of such spectra for methylcyclohexane between 132 and 295 K (the melting point is 147 K). To our knowledge, these are the only data in the literature that are taken across a sufficiently wide range of wavelengths and temperatures.…”

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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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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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“…[78] At the maximum the extinction coefficient is 2.8 x lo4 M-lcm-'. The spectrum for 3-methyloctane at 127 K, shown in Figure 8.4, peaks around 2 pm.…”

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confidence: 99%