TY - JOUR

T1 - An Updated View of Primary Ionization Processes in Polar Liquids

AU - Beregovaya, Irina V.

AU - Tretyakova, Irina S.

AU - Borovkov, Vsevolod I.

N1 - Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/12/2

Y1 - 2021/12/2

N2 - According to picosecond radiolysis data, primary radical cations in irradiated carbonates are very rapidly deprotonated. At the same time, analysis of the radiation-induced fluorescence from carbonate solutions indicates the formation of solvent-related radical cationic species with a relatively long lifetime. We use quantum chemical methods to develop a model of carbonate ionization that reconciles these conflicting data. Using ethylene carbonate as an example and assuming that its molecules exist in solution as a collection of dimeric associates, we show that both processes are the result of the loss of an electron from such dimers. This demonstrates that the generally accepted conceptualization of a primary ionization event, based on the idea of the formation of a radical cation of an individual molecule of an irradiated substance, requires revision in the case of polar aprotic liquids that tend to form molecular associates.

AB - According to picosecond radiolysis data, primary radical cations in irradiated carbonates are very rapidly deprotonated. At the same time, analysis of the radiation-induced fluorescence from carbonate solutions indicates the formation of solvent-related radical cationic species with a relatively long lifetime. We use quantum chemical methods to develop a model of carbonate ionization that reconciles these conflicting data. Using ethylene carbonate as an example and assuming that its molecules exist in solution as a collection of dimeric associates, we show that both processes are the result of the loss of an electron from such dimers. This demonstrates that the generally accepted conceptualization of a primary ionization event, based on the idea of the formation of a radical cation of an individual molecule of an irradiated substance, requires revision in the case of polar aprotic liquids that tend to form molecular associates.

UR - http://www.scopus.com/inward/record.url?scp=85120419070&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.1c03388

DO - 10.1021/acs.jpclett.1c03388

M3 - Article

C2 - 34807617

AN - SCOPUS:85120419070

VL - 12

SP - 11573

EP - 11577

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 47

ER -