V.I. Borovkov

Time-resolved electric field effects in recombination fluorescence as a method of studying primary radiation-chemical processes

Abstract A new approach is proposed to identify the recombining particles in irradiated hydrocarbon solutions. It is based on the observation of time-resolved effects of an electric field in recombination fluorescence. The experiments demonstrate the possibility of observing molecular ions, electrons and holes that participate in radiation track recombination. The recombination processes involving the aforementioned particles can be reasonably distinguished in summary fluorescence kinetics by choosing the corresponding field strength.

Radical cations of n-alkanes in irradiated solutions as studied by time-resolved magnetic field effects

The time-resolved magnetic field effect in the recombination fluorescence of spin-correlated radical ion pairs has been measured to study n-alkane radical cations in irradiated solutions at room temperature. The magnetic field effect was recorded as a ratio of fluorescence decay curves in the 0.1 T and zero magnetic fields for solutions of C8, C9, C10, C12, and C16 n-alkanes in n-hexane with addition of 3 × 10−5 M p-terphenyl-d 14. A distinct maximum at 10–30 ns followed by a slowly decaying plateau was observed for all the solutions. Simulation shows that the maximum corresponds to an unresolved ESR spectrum with the peak-to-peak line-width ranging from about 1.6mT to 0.5mT for C8 to C16 radical cations. The unresolved structure is believed to result from the hyperfine couplings with many protons of the radical cation, the increase in the number of interacting protons compared with low temperature matrices being caused by the methyl group rotation and conformational motion of the carbon chain. With increase in concentration of dissolved n-alkane, the maximum in the curves first moves to longer times and finally disappears; this was attributed to the narrowing of ESR spectrum contour due to degenerate electron exchange.

Microwave field effects on the time dependence of recombination fluorescence from non-polar solutions

Abstract A novel experimental setup to study the effect of microwave field on the kinetics of recombination fluorescence from nonpolar solutions irradiated with nanosecond X-ray pulses is described. Experiments on the observation of the microwave field effects in dodecane and hexane solutions are presented. The most favorable conditions for observation of the microwave induced quantum oscillations are found. The effect of spin locking was observed for the first time in the time-resolved microwave field effects. An efficient method to calculate the spin evolution of a radical pair in a microwave field taking into account relaxation is suggested. Analytical expressions for the microwave field effect in the limiting cases of large and small hyperfine splittings are given.

Radical ions with nearly degenerate ground state: Correlation between the rate of spin-lattice relaxation and the structure of adiabatic potential energy surface

Paramagnetic spin-lattice relaxation (SLR) in radical cations (RCs) of the cycloalkane series in liquid solution was studied and analyzed from the point of view of the correlation between the relaxation rate and the structure of the adiabatic potential energy surface (PES) of the RCs. SLR rates in the RCs formed in x-ray irradiated n-hexane solutions of the cycloalkanes studied were measured with the method of time-resolved magnetic field effect in the recombination fluorescence of spin-correlated radical ion pairs. Temperature and, for some cycloalkanes, magnetic field dependences of the relaxation rate were determined. It was found that the conventional Redfield theory of the paramagnetic relaxation as applied to the results on cyclohexane RC, gave a value of about 0.2 ps for the correlation time of the perturbation together with an unrealistically high value of 0.1 T in field units for the matrix element of the relaxation transition. The PES structure was obtained with the DFT quantum-chemical calculations. It was found that for all of the cycloalkanes RCs considered, including low symmetric alkyl-substituted ones, the adiabatic PESes were surfaces of pseudorotation due to avoided crossing. In the RCs studied, a correlation between the SLR rate and the calculated barrier height to the pseudorotation was revealed. For RCs with a higher relaxation rate, the apparent activation energies for the SLR were similar to the calculated heights of the barrier. To rationalize the data obtained it was assumed that the vibronic states degeneracy, which is specific for Jahn-Teller active cyclohexane RC, was approximately kept in the RCs of substituted cycloalkanes for the vibronic states with the energies above and close to the barrier height to the pseudorotation. It was proposed that the effective spin-lattice relaxation in a radical with nearly degenerate low-lying vibronic states originated from stochastic crossings of the vibronic levels that occur due to fluctuations of the interaction between the radical and the solvent. The magnitude of these fluctuations, ~100 cm(-1), determines the upper scale of the unperturbed splitting between the vibronic states, for which the manifestation of this paramagnetic relaxation mechanism could be expected. Our estimate for the relaxation rate derived using standard Landau-Zener model of nonadiabatic transitions at the level crossing agrees with the experimental data. This paramagnetic relaxation mechanism can also be operative in paramagnetic species of other types such as linear radicals, radicals with threefold degeneracy, paramagnetic centers in crystals, etc. It looks likely that the proposed SLR mechanism can be quenched by a fast vibrational relaxation in radicals.

Spin evolution of radical pair with radical containing two groups of equivalent magnetic nuclei

Analytical solution is obtained for time-resolved magnetic field effects (TR-MFE) on recombination fluorescence of radical-ion pair (RIP) containing radical ion with two groups of magnetically equivalent nuclei. The present theoretical approach is applied to three experimental systems: RIPs containing radical cations of 2,3-dimethylbutane, 2,2,6,6-tetramethylpiperidine, or diisopropylamine and radical anion of p-terphenyl-d14 in nonpolar alkane solutions. Good agreement between theory and experiment is found for all the three systems, hyperfine coupling constants of radical cations are obtained by fitting the experimental TR-MFE traces. The potential of the TR-MFE technique for studying radical ions with nonequivalent nuclei is discussed in detail. The wide applicability of the theoretical model and the experimental technique make them useful for studying short-lived radical species that are often beyond the reach of the conventional electron paramagnetic resonance spectroscopy.

Comparison of the Mobilities of Negative and Positive Ions in Nonpolar Solutions

The mobilities of organic radical ions of different molecular volumes have been determined in squalane and hexane solutions to study the influence of the ion charge sign on the ionic mobility in a weakly polar liquid. The relative mobility of geminate radical ions was measured using the method of time-resolved electric field effect in the recombination fluorescence. To determine the mobility of cations and anions separately, a trend in the value of the relative mobility was analyzed by varying the mobility of one of the geminate partners. The ratios between the mobilities of the anion and the cation of the same molecules were found to be about 1.1. It was shown that in liquid alkanes, the solvent electrostriction was the main factor determining a decrease in the mobility of an ion as compared to the parent neutral molecule. The strong dependence of the electrostrictive effect on the radius of the ionic solvation shell allows the observed difference between negative and positive charge carriers by a small but systematic difference in the effective radii of the ions to be explained.

Study of Spin-Correlated Radical Ion Pairs in Irradiated Solutions by Optically Detected EPR and Related Techniques

The strong Coulomb attraction and recombination dramatically shorten the lifetime of radical ion pairs generated by ionizing irradiation in organic solutions, which complicates the use of conventional EPR spectroscopy to study these short-lived radical ions. However, the recombination of the oppositely charged ions gives birth to a fluorescence response of the irradiated media. This response appears to depend on the same properties of the radical ions that are studied by EPR spectroscopy. The dependence can be revealed with an external magnetic field, thus allowing a quantitative study of hyperfine couplings, spin-orbit interaction, paramagnetic relaxation times of radical ions, whose lifetime can amount to only a few nanoseconds. In this chapter we consider experimental approaches, both steady-state and time-resolved, which are based on the registration of the fluorescence response influenced by an external magnetic field. These are Optically Detected EPR, MARY (Magnetically Affected Reaction Yield) spectroscopy, and the technique of Time-Resolved Magnetic Field Effect (TR MFE) in recombination fluorescence. A brief history, a theoretical background, methodological details, as well as some unique experimental results obtained with these techniques are discussed.

Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair

Abstract We suggest a convenient probe exciplex system for studies in radiation spin chemistry based on a novel acceptor-substituted diphenylacetylene, 1-(phenylethynyl)-4-(trifluoromethyl)benzene that has a very short fluorescence lifetime (<200 ps) and low quantum yield (0.01) of intrinsic emission, provides efficient electron capture in alkanes and efficient exciplex formation upon recombination in pair with DMA radical cation, while exhibiting a shifted to red exciplex emission band as compared to the parent system DMA – diphenylacetylene. After chemical, luminescent, radiation and spin-chemical characterization of the new system we used the magnitude of magnetic field effect in its exciplex emission band for experimental estimation of the fraction of spin-correlated radical ion pairs under X-irradiation with upper energy cutoff 40 keV in a set of 11 alkanes. For linear and branched alkanes magnetic field effects and the corresponding fractions are approximately 19–20% and 0.28, while for cyclic alkanes they are lower at 16–17% and 0.22, respectively.