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Electronic Structures of Formic Acid (HCOOH) and Formate (HCOO(-)) in Aqueous Solutions
Matthew A Brown1, Fernando Vila2, Martin Sterrer3
1†Institute for Chemical and Bioengineering, ETH Zürich, CH-8093 Zürich, Switzerland.
Abstract:
The electronic structures of formic acid (HCOOH) and formate (HCOO(-)) have been determined in aqueous solutions over a pH range of 1.88-8.87 using a combination of X-ray photoelectron spectroscopy (XPS), partial electron-yield X-ray absorption spectroscopy (PEY XAS), and density functional theory (DFT). The carbon 1s XPS measurements reveal a binding energy shift of -1.3 eV for deprotonated HCOO(-) compared with neutral HCOOH. Such distinction between neutral HCOOH and deprotonated HCOO(-) cannot be made based solely on the respective carbon K-edge PEY XA spectra. Independent of pH, the C1s → π* state excitations occur at 288.0 eV and may lead to the incorrect conclusion that the energy levels of the π* state are the same for both species. The DFT calculations are consistent with the experimental observations and show a shift to higher energy for both the occupied C1s (lower binding energy) and unoccupied π* orbitals of deprotonated HCOO(-) compared to neutral HCOOH in aqueous solutions.
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