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Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence. / Borovkov, Vsevolod; Taratayko, Andrey; Bessmertnykh, Alena et al.
In: Zeitschrift fur Physikalische Chemie, Vol. 231, No. 2, 01.02.2017, p. 311-323.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence
AU - Borovkov, Vsevolod
AU - Taratayko, Andrey
AU - Bessmertnykh, Alena
AU - Bagryansky, Victor
AU - Molin, Yuriy
PY - 2017/2/1
Y1 - 2017/2/1
N2 - It has been found that addition of alcohols (~0.1 M) to some liquid ketones and esters results in well-pronounced oscillations in the decay of the delayed fluorescence intensity from irradiated solutions. The analysis of the time-resolved magnetic field effects (TR MFEs) in the recombination fluorescence has shown that these oscillations are a manifestation of singlet-triplet transitions in spin-correlated radical ion pairs (RIPs) created by irradiation. Comparison with literature data indicates that the transitions are due to hyperfine couplings (HFCs) in the solvent radical anion (RA), stabilized due to the presence of alcohol molecules. In acetone, this stabilization effect has been observed for methanol, ethanol, 2-propanol, and, to a smaller extent, for tert-butanol. Similar effects have also been observed in diethyl ketone, ethyl acetate, and methyl propionate but not in methyl tert-butyl ketone and ethyl trimethylacetate. The results obtained indicate that the interaction between the radical anions (RAs) of carbonyl compounds and alcohol molecules is of importance in pulse radiolysis studies of organic liquids and their mixtures.
AB - It has been found that addition of alcohols (~0.1 M) to some liquid ketones and esters results in well-pronounced oscillations in the decay of the delayed fluorescence intensity from irradiated solutions. The analysis of the time-resolved magnetic field effects (TR MFEs) in the recombination fluorescence has shown that these oscillations are a manifestation of singlet-triplet transitions in spin-correlated radical ion pairs (RIPs) created by irradiation. Comparison with literature data indicates that the transitions are due to hyperfine couplings (HFCs) in the solvent radical anion (RA), stabilized due to the presence of alcohol molecules. In acetone, this stabilization effect has been observed for methanol, ethanol, 2-propanol, and, to a smaller extent, for tert-butanol. Similar effects have also been observed in diethyl ketone, ethyl acetate, and methyl propionate but not in methyl tert-butyl ketone and ethyl trimethylacetate. The results obtained indicate that the interaction between the radical anions (RAs) of carbonyl compounds and alcohol molecules is of importance in pulse radiolysis studies of organic liquids and their mixtures.
KW - Ionic hydrogen bond
KW - quantum beats
KW - radiolysis of organic solvents
KW - spin-correlated radical pairs
KW - ionic hydrogen bond
KW - ELECTRON-SPIN-RESONANCE
KW - METHANOL
KW - ACETONE
KW - RADIATION
KW - CATIONS
KW - SPECTROSCOPY
KW - PULSE-RADIOLYSIS
KW - PHOTOCHEMISTRY
KW - SPECTRA
UR - http://www.scopus.com/inward/record.url?scp=85012165187&partnerID=8YFLogxK
U2 - 10.1515/zpch-2016-0818
DO - 10.1515/zpch-2016-0818
M3 - Article
AN - SCOPUS:85012165187
VL - 231
SP - 311
EP - 323
JO - Zeitschrift fur Physikalische Chemie
JF - Zeitschrift fur Physikalische Chemie
SN - 0942-9352
IS - 2
ER -
ID: 9079898