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Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface
Published on: January 24, 2018
Electron spectroscopy for chemical analysis of liquids
Lukáš Tomaník1,2, Florian Trinter1, Petr Slavíček2
1Department of Molecular Physics, Fritz-Haber-Institut of the Max Planck Society Faradayweg 4-6 14195 Berlin Germany winter@fhi-berlin.mpg.de tomanikl@vscht.cz.
Abstract:
We present the first comprehensive, internally consistent analysis of core-level chemical shifts for aqueous-phase solutes using Electron Spectroscopy for Chemical Analysis of Liquids (ESCAL). An absolute binding-energy calibration enables high accuracy and cross-molecule comparability. The C 1s spectra of oxygenated aliphatic compounds display functional-group-specific shifts that increase with carbon oxidation state. Although these trends depart from gas- and solid-phase behavior, highlighting solvent and hydration effects, they correlate closely with calculated core-level orbital energies, providing a useful first-order predictor. We further resolve secondary, through-bond shifts over one and two bonds, the magnitudes of which depend sensitively on specific functional-group interactions (notably carboxylic acid and ketone motifs). Such element- and oxidation-state-specific structural information establishes the principles and reference data needed to build a predictive ESCAL database for liquid-phase structural and chemical analysis. The results will be contrasted with NMR studies.
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