Lifetimes of the solvated electron in liquid alcohols

Baxendale, J. H.; Wardman, Peter

doi:10.1139/v77-425

Cited by 5 publications

(18 citation statements)

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“…The studies in the 1970s and 1980s [19][20][21][22][23][24][25][26] showed that in dilute solutions of hydroxylic molecules (such as alcohols and water) in normal and branched alkanes, the electrons attach to pre-existing clusters S n (multimers) of these solute ( S) molecules. (2)…”

Section: Polar Solute Traps In Alkane Solventsmentioning

confidence: 99%

“…Individual alcohol and water molecules (the "monomers", n = 1) do not trap the excess electrons, and in very dilute (< 1-5 mM) alkane solutions, localized electrons still reside in solvent traps. By contrast, alcohol clusters present in more concentrated solutions [19][20][21][22][23][24][25][26] bind the electrons quite strongly. H-bonded dimers and higher multimers of hydroxylic molecules form spontaneously in alkanes by reactions (4)…”

Section: Polar Solute Traps In Alkane Solventsmentioning

confidence: 99%

“…Mozumder's paper 18 outlining this scenario stimulated a brief flurry of experimental activity. [19][20][21][22][23][24][25][26][27] It was expected that small electron clusters, as opposed to solvated electrons in neat liquids, would be simple to study and to model. (Similar expectations were later nurtured for gas phase cluster anions).…”

Section: Introductionmentioning

confidence: 99%

“…(Similar expectations were later nurtured for gas phase cluster anions). Electron localization in dilute solutions of water and alcohols in liquid [19][20][21][22][23][24][25][26] and vitreous e.g., 27 alkanes was studied using pulse radiolysis -transient absorbance (TA) spectroscopy, 19,20,23,24,27 time-resolved conductivity, [21][22][23][24][25] and optically detected magnetic resonance (ODMR). 26 The results obtained in these studies hinted at a complex picture of electron dynamics and the interest in mixed solvents quickly waned.…”

Section: Introductionmentioning

confidence: 99%

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Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution

Shkrob

Sauer

2005

J. Phys. Chem. A

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Experimental observations are presented on condensed-phase analogues of gas-phase dipole-bound anions and negatively charged clusters of polar molecules. Both monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis-transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained, and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. The acetonitrile monomer is shown to solvate the electron by its methyl group, just as the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the predominant electron trap is a trimer or a tetramer, and the binding energy of this solute trap is ca. 0.8 eV. Trapping by smaller clusters is opposed by the entropy that drives the equilibrium toward the electron in a solvent trap. For alcohol monomers, the trapping does not occur; a slow proton-transfer reaction occurs instead. For the acetonitrile monomer, the trapping is favored energetically, but the thermal detachment is rapid (ca. 1 ns). Our study suggests that a composite cluster anion consisting of a few polar molecules imbedded in an alkane "matrix" might be the closest gas-phase analogue to the core of solvated electron in a neat polar liquid.

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Section: Polar Solute Traps In Alkane Solventsmentioning

confidence: 99%

Section: Polar Solute Traps In Alkane Solventsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution

Shkrob

Sauer

2005

J. Phys. Chem. A

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“…(Notethat 7,isustdratherthanr,beCBusethesolvation 298The Journal of Physical Chemistry, Vol. 97, No 2,. 1993 …”

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confidence: 99%

Picosecond dynamics of benzophenone anion solvation

Lin¹,

Jonah²

1993

J. Phys. Chem.

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The dynamics of benzophenone anion solvation in alcohols are studied by pulse-radiolysis techniques. The solvation process is characterized by the blue shift of the transient absorption spectrum of the anion and is faster for the smaller alcohols. The anion is solvated more slowly than the electron in the same solvent, but the solvation times of both are similar to 7 2 , the solvent dielectric relaxation time. The familiar phenomenological "two-state" model of solvation was found to be inappropriate for describing the anion solvation process. A multistate process appears to be a more appropriate description. We modeled the kinetics of the spectral relaxation. In most cases, nearly quantitative agreement between the calculated and observed spectra is achieved.The characteristic relaxation times for the alcohol solvents around the anions were also reproduced. I, IatroductionThe solvent plays multiple roles in determining the course of condensed-phase chemical reactions. The solvent can remove energy from the reactants; it can confine reactants into regions in space (cage effects); and it can stabilize or destabilize the creation of charges. Solventsharge interactions are explored in this paper. A framework for this exploration can be created by posing two important questions. How do solvent molecules react to the sudden creation of a charged species, and what microscopic factors of the charged molecule structure and solvent molecule struture control this response? In the past decade, a number of researchers have employed picosecond time-resolved absorption and emission spectroscopy to probe the dynamics of the solvation of an electron or the solvation of a large molecular dipole created in a polar liquid.'-* Both the size of the spectral shifts and the time scale of these shifts have been probed theoretically.+' * Our understanding of the nature of the solvation has been deepened by these studied. In a recent publication, Jortner reviewed the status of the solvation experiments and divided the work into three classes: (1) solvation of the electron, (2) solvation of a molecular dipole, and (3) extraction of information about the solvation process from the rates of electron-transfer reactions." However, the solvation dynamics of ions in polar solution have not beeen experimentally measured. While structural data exist for small ions in water, neither the structure nor the dynamics of the solvation of larger ions have been studied. This behavior is of prime interest to physical chemists and is important for understanding many chemical and biological processes.There have been few studies of the time-dependent solvent reorganization processes around an ion that is created quickly compared to the relaxation time of the solvent. In this work, we present a pulse-radiolytic study of the solvation of a large aromatic anion in a seriesof primary alcohols. The system selected for this study was benzophenone anion, because its absorption spectrum isstronglyshifted by theso1vent;it issolubleat highconcentration; and its absorpti...

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The decay of solvated electrons in irradiated liquid alcohols

Baxendale

Wardman

1984

Radiation Physics and Chemistry (1977)

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Lifetimes of the solvated electron in liquid alcohols

Cited by 5 publications

References 1 publication

Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution

Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution

Picosecond dynamics of benzophenone anion solvation

The decay of solvated electrons in irradiated liquid alcohols

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