MARY-detected ESR spectrum of solvent radical cations (holes) in squalane

Tadjikov, B.M.; Stass, Dmitrii V.; Усов, О. А.; Molin, Yu. N.

doi:10.1016/s0009-2614(97)00587-3

Cited by 18 publications

(23 citation statements)

References 14 publications

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“…This study supports previous observation of rapid scavenging of cyclooctane holes by aromatic solutes in the initial stage of radiolysis [35]. Both in the squalane and cyclooctane, the natural lifetime of the high mobility solvent hole is less than 20 ns [24,[27][28][29][30][31][32][33][34][35]. It is still unclear whether this lifetime is limited by the inherent instability of the solvent holes or by their reactions with impurity.…”

Section: S S S So O O Ol L L Lv V V Ve E E En N N Nt T T T H supporting

confidence: 88%

“…Analogous results were obtained for other systems (alcohols, benzene) [32]. Since ODMR and related studies indicate that for squalane holes the spin-lattice relaxation is longer than their decay [24,28,29], this loss of spin coherence cannot be accounted for by spin randomization of primary pairs due to magnetic interactions in the charges. It appears that the initial state of the electron-hole pair is not purely singlet.…”

supporting

confidence: 72%

“…In the squalane, rapid electron-transfer reactions of solvent holes with low-IP solutes were observed using transient absorbance spectroscopy and magnetic resonance [24]. Fast diffusion and highrate scavenging reactions of the squalane holes were also observed using magnetic levelcrossing [28,29] and quantum beat [29] spectroscopies (see reviews [30] and [31] for the principles of these recently developed spin coherence spectroscopies). Rapid scavenging reactions were also found to account for the anomalies in the magnetic field effect observed for delayed solute fluorescence induced by VUV excitation of squalane [32,33].…”

Section: S S S So O O Ol L L Lv V V Ve E E En N N Nt T T T H mentioning

confidence: 99%

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Radiation Chemistry of Organic Liquids: Saturated Hydrocarbons

2004

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Section: S S S So O O Ol L L Lv V V Ve E E En N N Nt T T T H supporting

confidence: 88%

supporting

confidence: 72%

Section: S S S So O O Ol L L Lv V V Ve E E En N N Nt T T T H mentioning

confidence: 99%

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Radiation Chemistry of Organic Liquids: Saturated Hydrocarbons

2004

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“…The dependence of the LC-derived feature on the RP lifetime is very well-known in spin chemistry: the field dependence of the RP recombination yield exhibits sharp peaks originating from LCs. [59][60][61][62] In our case the dependence on relevant RP parameters is more complex, but the general behavior is the same. The width of the feature coming from an LAC is determined by the actual width of the LAC region and does not depend strongly on k sc .…”

Section: Isotropic Case J Ex =mentioning

confidence: 75%

Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

Sosnovsky

Jeschke

Matysik

et al. 2016

The Journal of Chemical Physics

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Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign rules. Thus, LCs/LACs provide a consistent description of CIDNP in both liquids and solids with the prospect of exploiting it for the analysis of short-lived radicals and for optimizing the polarization level.

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“…We forewarn the reader that the formation of high-mobility holes is not peculiar to these four cycloalkanes: for instance, cyclooctane [61], squalane [62,63,64], and CCl 4…”

Section: Solvent Radical Cations In Liquid Cycloalkanesmentioning

confidence: 99%

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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MARY-detected ESR spectrum of solvent radical cations (holes) in squalane

Cited by 18 publications

References 14 publications

Radiation Chemistry of Organic Liquids: Saturated Hydrocarbons

Radiation Chemistry of Organic Liquids: Saturated Hydrocarbons

Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

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

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