title: Ultrafast Decay of the Solvated Electron in a Neat Polar Solvent: The Unusual Case of Propylene Carbonate.
abstract: The behavior of carbonates is critical for a detailed understanding of aging phenomena in Li-ion batteries. Here we study the first reaction stages of propylene carbonate (PC), a cyclical carbonate, by picosecond pulse radiolysis. An absorption band with a maximum around 1360 nm is observed at 20 ps after the electron pulse and is shifted to 1310 nm after 50 ps. This band presents the features of a solvated electron absorption band, the solvation lasting up to 50 ps. Surprisingly, in this polar solvent, the solvated electron follows an ultrafast decay and disappears with a half time of 360 ps. This is attributed to the formation of a radical anion PC(-•). The yield of the solvated electron is low, suggesting that the radical anions are mainly directly produced from presolvated electrons. These results demonstrate that the initial electron transfers mechanisms are strongly different in linear compared with cyclical carbonates.
authors.affiliation: CEA/Saclay, Université Paris-Saclay, DSM/IRAMIS/NIMBE UMR 3685 CNRS/CEA, LIONS, Bât. 546, F-91191 Gif-sur-Yvette Cedex, France.
authors.forename: Sophie
authors.initials: S
authors.lastname: Le Caër
authors.affiliation: CEA/Saclay, Université Paris-Saclay, DSM/IRAMIS/NIMBE UMR 3685 CNRS/CEA, LIONS, Bât. 546, F-91191 Gif-sur-Yvette Cedex, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Ortiz
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS, Université Paris Sud, Université Paris-Saclay, Bât. 349, F-91405 Orsay Cedex, France.
authors.forename: Jean-Louis
authors.initials: JL
authors.lastname: Marignier
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS, Université Paris Sud, Université Paris-Saclay, Bât. 349, F-91405 Orsay Cedex, France.
authors.forename: Uli
authors.initials: U
authors.lastname: Schmidhammer
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS, Université Paris Sud, Université Paris-Saclay, Bât. 349, F-91405 Orsay Cedex, France.
authors.forename: Jacqueline
authors.initials: J
authors.lastname: Belloni
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS, Université Paris Sud, Université Paris-Saclay, Bât. 349, F-91405 Orsay Cedex, France.
authors.forename: Mehran
authors.initials: M
authors.lastname: Mostafavi