TY - JOUR

T1 - Spin-correlated radical ion pairs generated in liquid haloalkanes using high-energy radiation

AU - Borovkov, V. I.

PY - 2018/9/20

Y1 - 2018/9/20

N2 - 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.

AB - 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.

KW - IRRADIATED POLY(METHYL METHACRYLATE)

KW - PHOTO-ELECTRON SPECTRA

KW - PULSE-RADIOLYSIS

KW - MAGNETIC-FIELD

KW - AROMATIC-HYDROCARBONS

KW - CHLOROMETHYL RADICALS

KW - NONPOLAR-SOLVENTS

KW - RESONANCE

KW - CATIONS

KW - RECOMBINATION

UR - http://www.scopus.com/inward/record.url?scp=85053346790&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcb.8b06884

DO - 10.1021/acs.jpcb.8b06884

M3 - Article

C2 - 30132333

AN - SCOPUS:85053346790

VL - 122

SP - 8750

EP - 8762

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 37

ER -