Identification of Transient Radical Anions (LiClO 4 ) n − (n = 1−3) in THF Solutions: Experimental and Theoretical Investigation on Electron Localization in Oligomers

Jun Ma (1) , Pierre Archirel (1) , Pascal Pernot (1) , Uli Schmidhammer (1) , Sophie Le Caër (2) , Mehran Mostafavi (1)

1 LCPO - Laboratoire de Chimie Physique D'Orsay
2 LIONS - Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire

Picosecond pulse radiolysis measurements of tetrahydrofuran (THF) solutions containing LiClO 4 over a wide range of concentration are performed to investigate the formation of transient species. The 35 Cl NMR measurements of these solutions prior to irradiation show that the salt is in the form of (LiClO 4) n oligomers. Kinetics and transient absorption spectra of intermediates in each solution are obtained on the time scale from 10 to 3800 ps. A global spectro-kinetic matrix of the data is analyzed by the multicurve resolution alternated least-squares (MCR-ALS) method. It shows the presence of 3 transient species induced by electron pulse, in addition to the solvated electron. A hybrid Monte Carlo/DFT molecular simulation method is elaborated, using the MPW1K functional for the configuration sampling and B3LYP for the spectra calculations. The maximum of the absorption band of the monomer (LiClO 4) − , dimer (LiClO 4) 2 −

Domaines: Matériaux

Jun Ma, Pierre Archirel, Pascal Pernot, Uli Schmidhammer, Sophie Le Caër, et al.. Identification of Transient Radical Anions (LiClO 4 ) n − (n = 1−3) in THF Solutions: Experimental and Theoretical Investigation on Electron Localization in Oligomers. Journal of Physical Chemistry B, 2016, 120, pp.773-784. ⟨10.1021/acs.jpcb.5b11315⟩. ⟨cea-01278020⟩