Exploiting time-resolved magnetic field effects for determining radical ion reaction rates

Bessmertnykh, Alena; Borovkov, V. I.; Bagryansky, V. A.; Molin, Yu. N.

doi:10.1016/j.cplett.2016.06.011

Cited by 2 publications

(3 citation statements)

References 21 publications

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“…For discussion in the paper, we chose the data obtained with the CAMB3LYP calculations. In the case of the RC of 2,2,4,4,6,8,8-heptamethylnonane, whose structure is somewhat similar to that of PIB, the use of this functional led to the value of Δ H pp ≈ 3.4 mT that was close to the experimental , ones (see Table S1 in the Supporting Information).…”

Section: Methodssupporting

confidence: 59%

Primary Radical Cations in Irradiated Poly(isobutylene)

et al. 2020

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Using the method of time-resolved magnetic field effect in radiation-induced fluorescence, primary radical cations (RCs) in irradiated poly(isobutylene) (PIB) have been detected for the first time. A comparison of experimental results with the data of quantum chemical calculations suggests that the initial geometry of the ionized fragment of the PIB molecule is close to the geometry of the neutral polymer in the trans–gauche–trans–gauche conformation. The spin density of the RC in this geometry is delocalized over more than 10 polymer units, and the width of the RC’s EPR spectrum is about ΔH pp ≈ 1.3 mT. At a temperature of 273 K and lower, the lifetime of the primary RCs with the delocalized spin density exceeds 10 ns. The structural relaxation of the RCs results in the spin density localization on a single C–C bond, which is extended to nearly 0.2 nm, and in the increase in the EPR spectrum width to ΔH pp ≈ 2.4 mT. It looks likely that this intramolecular structural relaxation is coupled strongly with those types of molecular motions that determine the process of dielectric β-relaxation in the polymer.

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Section: Methodssupporting

confidence: 59%

Primary Radical Cations in Irradiated Poly(isobutylene)

et al. 2020

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“…Figure shows the experimental TR MFE curves obtained in the range of bDOTP concentrations from 3 to 30 mM along with the simulation results. In line with that described in Section , the simulation has been performed using eqs S1, S2, and S4–S6, taking the nonstationary effects in bimolecular reactions into account …”

Section: Results and Discussionmentioning

confidence: 99%

“…The TR MFE method can also be applied if one of the partners of the spin-correlated RIP transforms into another radical ion, allowing estimation of the rate of transformation . The corresponding expressions used to calculate the MFE curves in such a reaction, taking into account the nonstationary effects in bimolecular reactions, are given in the Supporting Information (eqs S1, S2, and S4).…”

Section: Materials and Methodsmentioning

confidence: 99%

Spin-Correlated Radical Ion Pairs Generated in Liquid Haloalkanes Using High-Energy Radiation

Borovkov

2018

J. Phys. Chem. B

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The probability of formation of spin-correlated secondary radical ion pairs (RIPs) in diluted solutions of charge acceptors in irradiated haloalkanes is believed to be extremely low due to the dissociative attachment of excess electrons to solvent molecules. Contrary to this, it has been found that spin-correlated RIPs can be formed upon irradiation in some liquid chloroalkanes with yield sufficient to observe the recombination fluorescence of the RIP's partners. This allowed the study of primary radical cations (RCs) as well as radical ionic states of molecules dissolved in haloalkanes using the method of time-resolved magnetic field effect (TR MFE) in radiation-induced fluorescence. With this method, the magnetic resonance characteristics of the solvent RCs in a series of liquid haloalkanes were examined for the first time. For the 1,2-dichloroethane RC, the rate of scavenging by solute molecules and the dominant mechanisms of paramagnetic relaxation were determined. Polysulfone and poly(ethyl methacrylate) were used to demonstrate that due to their high dissolving ability, chloroalkanes can be exploited as solvents to study the magnetic resonance characteristics of radical ionic states of polymeric molecules in solutions with the TR MFE method.

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Exploiting time-resolved magnetic field effects for determining radical ion reaction rates

Cited by 2 publications

References 21 publications

Primary Radical Cations in Irradiated Poly(isobutylene)

Primary Radical Cations in Irradiated Poly(isobutylene)

Spin-Correlated Radical Ion Pairs Generated in Liquid Haloalkanes Using High-Energy Radiation

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