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• W2079818152 abstract "Two and three pulse photolysis experiments on terahydrofuran (THF) solutions of Na−, utilizing hyperspectral probing, are described. The objective is to probe the extent and duration of energetic correlations between the primary charge transfer to solvent (CTTS) fragments which are an e− and Na0. The latter is characterized by an intense visible absorption spectrum with fine structure reflecting the atom’s immediate solvent environment. Pump-probe experiments with ∼6fs pulses show that for the majority of irradiated ions, the electron ejection and production of unperturbed Na0 is effectively over in ∼15fs, with no precursors. Three pulse experiments further demonstrate this to be true for nearly all ions irradiated at 3eV. Thus, the 400nm data provide a detailed spectral record of the formation and subsequent solvation and polarization of neutral sodium bubbles in THF. Measures are presented for parametrizing the ensuing spectral evolution. In contrast, exciting at 1.5eV, the red edge of the CTTS band leads to charge transfer with less than unity quantum efficiency. The complementary fraction of absorbing ions is photostable at 800nm, presumably due to preferential solvent stabilization. Prompt secondary irradiation at 2μm can complete ionization of that population leading to additional generation of Na0 but exhibiting much more pronounced spectral structure. Thus, at low photon energies, a short lived correlated and bound electronic excited state is produced with significant yield. These results are discussed in terms of classical models for CTTS spectra, as well as more recent simulations and experiments concerning CTTS in this and other related systems." @default.
• W2079818152 created "2016-06-24" @default.
• W2079818152 creator A5029210279 @default.
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• W2079818152 date "2008-07-23" @default.
• W2079818152 modified "2023-09-27" @default.
• W2079818152 title "Na− photolysis in THF: Charge transfer to solvent studied from the donors perspective in <10fs detail" @default.
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• W2079818152 doi "https://doi.org/10.1063/1.2946701" @default.
• W2079818152 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18681655" @default.
• W2079818152 hasPublicationYear "2008" @default.
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