Effect of pressure on the electron mobility in liquid benzene and toluene

Itoh, Kengo; Holroyd, Richard A.

doi:10.1021/j100388a020

Cited by 34 publications

(48 citation statements)

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“…46 A similar situation is expected in solid polystyrene if we assume that the phenyl groups in PS have the same negative electron affinity as benzene and toluene. 47 For example, in a 30 mM Py/PS film, the excimer absorption at 490 nm was sufficiently reduced, and the pyrene anion absorption was dominant enough for us to measure the anion formation rate k f g 2.5 × 10 9 s -1 ( Table 1). The rate constant of the reaction between quasi-free electrons and pyrene molecules is estimated to be not less than 8.0 × 10 10 M -1 s -1 .…”

Section: Formation Of Solute Radical Ions Solute Anion Radicalsmentioning

confidence: 99%

Energy Transfer via Ionic Processes in Polymer Films Irradiated by 0.4 MeV Electrons

and

Thomas

1996

J. Phys. Chem.

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Radiation-induced processes in polymer films have been studied by pulse radiolysis using transient spectroscopic methods. A comparison with low-energy photoexcitation shows that singlet and triplet excited states of aromatic polymers produced by high-energy irradiation are mainly derived from geminate recombination between the polymer radical cations and the excess electrons. A simultaneous production of singlet and triplet excited states, radical cations, and radical anions of aromatic solutes doped in polystyrene was observed on static quenching of the polystyrene excimer. By use of pyrene as the spectroscopic probe, the absolute yields of the pyrene transient species in the polymer right after the pulse were measured as G( 1 Py * ) ≈ 0.8, G( 3 Py * ) ≈ 1.1, G(Py •+ ) ≈ 1.5, and G(Py •-) ≈ 1.5 at [Py] ) 100 mM. The large ion yields indicate an efficient charge generation in the nonpolar polymer matrix. Charge-scavenging experiments further reveal the ionic origin of the solute excited states. In the case of complete electron scavenging in poly(vinylbenzyl chloride), only the strong absorption band characteristic of the pyrene radical cations was observed. Both excited states and radical cations of solutes exhibit resolvable formation rates that increase with the solute concentration. An ionic mechanism of energy transfer is proposed to account for the formation of radical anions, radical cations, and excited states (S 1 and T 1 ) of solute molecules, respectively, from the electron scavenging, the positive charge transfer, and the secondary charge recombination reactions. Positive charge migration in polymer matrices is suggested to be responsible for the fast (∼2 ns) charge recombination and charge transfer reactions over large distances. The migration constant of the mobile positive charge is estimated from the charge transfer reaction rates to be Λ h ≈ 6.0 × 10 -5 cm 2 /s in polystyrene and poly(vinylbenzyl chloride). Numerical simulation of the experimental data using a single ion pair model shows that on average electrons are ejected ∼60 Å away from the parent cations in solid polystyrene and that ∼87% of the polystyrene excimer is derived from the primary geminate ion recombination. The effects of polymerization on charge separation and transport are discussed from an examination of the radiolytic responses of different polymers compared to those of their model compounds.

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Section: Formation Of Solute Radical Ions Solute Anion Radicalsmentioning

confidence: 99%

Energy Transfer via Ionic Processes in Polymer Films Irradiated by 0.4 MeV Electrons

and

Thomas

1996

J. Phys. Chem.

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“…respectively [45]) is very close to that in hexafluorobenzene (0.11 eV [41]), despite a large difference in their EA g ; the corresponding anion mobilities are also comparable.…”

Section: /12/04mentioning

confidence: 59%

“…The conductivity studies also indicate that there is no volume change associated with the dimerization [45].…”

Section: /12/04mentioning

confidence: 91%

See 1 more Smart Citation

Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A Critical Review

Shkrob

Sauer

2004

ChemInform

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Abstract.While ionization of some polyatomic molecular liquids (such as water and aliphatic alcohols) yields so-called "solvated electrons" in which the excess electron density is localized in the interstices between the solvent molecules, most organic and inorganic liquids yield radical anions and cations in which the electron and spin densities reside on the solvent molecule or, more commonly, a group of such molecules. The resulting multimer ions have many unusual properties, such as high rates of diffusive hopping. The "solvated electron" can be regarded as a variant of a multimer radical anion in which the charge, while perturbing the solvent molecules, mainly resides in the space between these molecules. We give several examples of less known modes for electron localization in liquids that yield multimer radical anions (such as C 6 F 6 , benzene, acetonitrile, carbon disulfide and dioxide, etc.) and holes localization in liquids that yield multimer radical cations (such as cycloalkanes). Current understanding of the reaction properties for these high-mobility solvent radical anions and cations is discussed.

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“…The mobility observed at high pressure for toluene is 0.06 cm"Ns, [178] for benzene is I 0.08 cm2Ns, [178] for m-xylene and o-xylene 0.06 and 0.04 cm2Ns, respectively. [159] Transport at high pressure is believed to occur by hopping:…”

Section: E Efective Mass (M *)mentioning

confidence: 91%

Electrons in Nonpolar Liquids

Holroyd¹

2003

Charged Particle and Photon Interactions With Matter

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Effect of pressure on the electron mobility in liquid benzene and toluene

Cited by 34 publications

References 0 publications

Energy Transfer via Ionic Processes in Polymer Films Irradiated by 0.4 MeV Electrons

Energy Transfer via Ionic Processes in Polymer Films Irradiated by 0.4 MeV Electrons

Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A Critical Review

Electrons in Nonpolar Liquids

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