Electron Mobilities and Ranges in Liquid Hydrocarbons: Cyclic and Polycyclic, Saturated and Unsaturated Compounds

Shinsaka, Kyoji; Dodelet, Jean‐Pol; Freeman, Gordon R.

doi:10.1139/v75-385

Cited by 32 publications

(10 citation statements)

References 13 publications

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“…At lower temperatures the larger activation energy of electron migration is probably due to the formation of deeper traps for the solvated electron. Similar behavior has been observed in other olefins (27 For personal use only.…”

Section: Free Ioit Yiells Aitd Peizetratioit Ranges C?jsupporting

confidence: 85%

“…27) can be attributed to a relatively large negative value of d(Vo -p)/dT. The energy Vo of the conduction band presumably behaves normally, but the energy of the localized state might decrease due to increasing involvement of a negative ion state as the temperature is lowered (27).…”

Section: Free Ioit Yiells Aitd Peizetratioit Ranges C?jmentioning

confidence: 99%

“…An effect other than polarity must explain the low mobilities in the two olefins. One possibility is the participation of transient negative ions (27).…”

Section: Experimental Values Frommentioning

confidence: 99%

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Molecular structure effects on electron ranges and mobilities in liquid hydrocarbons: chain branching and olefin conjugation: mobility model

Dodelet¹,

Shinsaka²,

Freeman³

1976

Can. J. Chem.

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. Can. J. Chem. 54, 744 (1976). The effect of molecular structure on electron behavior in liquids was studied by measuring secondary electron penetration ranges bGP and thermal electron mobilities II, in substituted methanes and ethylenes. The penetration ranges are smaller (energy transfer cross sections are larger) when the alkane molecules are less rigid. It was confirmed that the epithermal electron energy transfer interaction radius in a liquid phase alkane molecule is limited to two C-C bonds in series. This modifies the earlier noted correlation between b, , and the degree of sphericity of the molecules. For example, the density normalized range b,,d in the relatively sphere-like tetraethylmethane (54 X lo-* g/cm2) is more similar to that in the distinctly nonspherical diethylmethane (11-pentane, 43 X g/cm2) than to that in the sphere-like tetramethylmethane (126 X g/cm2). Tetraethylmethane is too large for the entire molecule to interact with an electron in the liquid phase, and the possibility of rotations about the C-C bonds in the ethyl groups makes the molecule less rigid. Electrons sense these relatively sphere-like molecules to be similar to those of a 11-alkane. Connecting tert-butyl groups to olefinic or acetylenic carbons creates sphere-like quasi neopentyl groups which greatly enhance electron ranges in the unsaturated compounds. In conjugated olefins cis-trans effects are largely overshadowed by the general efficiency of these compounds as electron energy sinks. The earlier noted correlation between be, and u, contains fine structure. For a given value of bGP, 11, increases in the order 11-alkane < cyclo or branched alkane < olefin. Electron mobilities are interpreted in terms of a model that contains a Gaussian distribution of solvated electron state energies, a conduction band, and thermally activated transitions between them. The model is a combination of our treatment of electrons in ethers and Schiller's treatment of electrons in hydrocarbons. The percolation model does not provide a sufficiently complete interpretation of electron migration in hydrocarbons.J.-P. DODELET, K. SHINSAKA et G. R . FREEMAN. Can. J. Chem. 54,744 (1976). L'effet de la structure molCculaire sur le comportement des Clectrons en exces dans les liquides a Ct C Ctudie en mesurant, pour differentes substitutions du mithane et de l'Cthylkne, le parcours des Clectrons secondaires, bo, et les mobilitks des Clectrons thermalises, 11,. Lorsque les molkules d'alcanes perdent leur rigiditC, les parcours Clectroniques sont plus courts. La probabilitC de transfert d'knergie par 1'Clectron Cpithermique est donc plus importante. Le rayon d'interaction de ce dernier avec les molkules d'alcanes a CtC confirm6 h deux liens C-C en strie. Ceci modifie la correlation prCcCdente entre bGp et le degrC de sphericit6 des molCcules. Par exemple, le parcours, normalis6 pour la densite, (bGpri = 54 X g/cm2) dans le tetraCthylmCthane resemble plus au parcours Clectronique dans le 11-pentane (43 X g/cm2) qu'i celui dans le tetramtthylmCthane (...

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Section: Free Ioit Yiells Aitd Peizetratioit Ranges C?jsupporting

confidence: 85%

Section: Free Ioit Yiells Aitd Peizetratioit Ranges C?jmentioning

confidence: 99%

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Molecular structure effects on electron ranges and mobilities in liquid hydrocarbons: chain branching and olefin conjugation: mobility model

Dodelet¹,

Shinsaka²,

Freeman³

1976

Can. J. Chem.

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“…A decrease of the activation energy at higher temperature was obtained for ethane while the data for rz-pentane show the opposite behavior. These two cases are also typical for a number of other liquids (16,22,26 energies were observed and the electron mobility in neopentane or tetramethylsilane was approximately independent of temperature in the range of temperature given in Table 1. …”

Section: The Effect Of Temperaturesupporting

confidence: 56%

Electron mobility in nonpolar liquids: the effect of molecular structure, temperature, and electric field

Schmidt¹

1977

Can. J. Chem.

135

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A survey is given on the mobility of excess electrons in liquid hydrocarbons and related compounds. It was found that the mobility is strongly influenced by the molecular structure of the liquid, by the temperature, and by the electric field strength. The mobility in hydrocarbons increases as the shape of the molecule approaches a sphere. The temperature coefficient is positive in most liquids over a limited temperature although exceptions have been observed in liquid methane. The field dependence of the mobility in high mobility liquids (>10 cm2V−1s−1) showed a decrease of the mobility at higher field strengths while in low mobility liquids (<1 cm2V−1s−1) it showed an increase. These results are discussed on the basis of the extended and the localized electron models. The predictions of these theories are compared with the experimental results and conclusions on the validity of the underlying assumptions are drawn.

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“…Doubts arising on the question as to whether spectrum II in Fig. 3 is to be assigned to radical anions of benzene can be discarded in so far as according to Holroyd [12] and Freeman et al [13] thermalized electrons do not react with benzene in non-polar solvents, such as cyclohexane, at room temperature.…”

Section: Discussionmentioning

confidence: 99%

Two Photon Ionization of Benzene in Methanol and Cyclohexane Solution

Tagawa¹,

Beck²,

Schnabel³

1982

Zeitschrift Für Naturforschung A

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Electron Mobilities and Ranges in Liquid Hydrocarbons: Cyclic and Polycyclic, Saturated and Unsaturated Compounds

Cited by 32 publications

References 13 publications

Molecular structure effects on electron ranges and mobilities in liquid hydrocarbons: chain branching and olefin conjugation: mobility model

Molecular structure effects on electron ranges and mobilities in liquid hydrocarbons: chain branching and olefin conjugation: mobility model

Electron mobility in nonpolar liquids: the effect of molecular structure, temperature, and electric field

Two Photon Ionization of Benzene in Methanol and Cyclohexane Solution

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