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Electronic Rearrangement upon the Hydrolyzation of Aqueous Formaldehyde Studied by Core-Electron Spectroscopies.

Ottosson, Niklas LU ; Aziz, Emad F; Bergersen, Henrik LU ; Pokapanich, Wandared; Öhrwall, Gunnar; Svensson, Svante LU ; Eberhardt, Wolfgang and Björneholm, Olle (2008) In The Journal of Physical Chemistry Part B 112(51). p.16642-16646
Abstract
We have combined near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to study the electronic rearrangement associated with the hydrolyzation of formaldehyde to methanediol in aqueous solution. The spectra are contrasted against those of aqueous formamide and urea, which are structurally similar but do not undergo hydrolysis in solution. We have recently demonstrated that the hydrolyzation of formaldehyde is manifested in the oxygen 1s NEXAFS spectrum by the disappearance of the oxygen 1s --> pi* absorption line. This is a characteristic signature that the CO double bond has been broken. In the present study we extend our investigation to include carbon 1s NEXAFS and XPS spectra of... (More)
We have combined near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to study the electronic rearrangement associated with the hydrolyzation of formaldehyde to methanediol in aqueous solution. The spectra are contrasted against those of aqueous formamide and urea, which are structurally similar but do not undergo hydrolysis in solution. We have recently demonstrated that the hydrolyzation of formaldehyde is manifested in the oxygen 1s NEXAFS spectrum by the disappearance of the oxygen 1s --> pi* absorption line. This is a characteristic signature that the CO double bond has been broken. In the present study we extend our investigation to include carbon 1s NEXAFS and XPS spectra of the three solutions. The carbon NEXAFS spectra show the C 1s --> pi* absorption line for each solute except for formaldehyde. Moreover, the carbon 1s photoelectron spectra exhibit a single peak for each solute. These observations point to a near complete hydrolyzation of formaldehyde, whereas formamide and urea remain intact in the solution. The analysis is further supported by density functional theory (DFT) calculations, showing a C 1s chemical shift of approximately 1.0 eV between hydrolyzed and nonhydrolyzed forms, which would give distinguishable features in the photoemission spectrum, if coexisting forms were present in the solutions. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
112
issue
51
pages
16642 - 16646
publisher
The American Chemical Society
external identifiers
  • wos:000261835100051
  • pmid:19055383
  • scopus:58149144552
ISSN
1520-5207
DOI
10.1021/jp806210m
language
English
LU publication?
yes
id
d49a7668-90f2-4b68-b81f-7a9fc83d3a6a (old id 1276478)
date added to LUP
2009-01-16 09:44:25
date last changed
2017-01-01 06:03:42
@article{d49a7668-90f2-4b68-b81f-7a9fc83d3a6a,
  abstract     = {We have combined near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to study the electronic rearrangement associated with the hydrolyzation of formaldehyde to methanediol in aqueous solution. The spectra are contrasted against those of aqueous formamide and urea, which are structurally similar but do not undergo hydrolysis in solution. We have recently demonstrated that the hydrolyzation of formaldehyde is manifested in the oxygen 1s NEXAFS spectrum by the disappearance of the oxygen 1s --> pi* absorption line. This is a characteristic signature that the CO double bond has been broken. In the present study we extend our investigation to include carbon 1s NEXAFS and XPS spectra of the three solutions. The carbon NEXAFS spectra show the C 1s --> pi* absorption line for each solute except for formaldehyde. Moreover, the carbon 1s photoelectron spectra exhibit a single peak for each solute. These observations point to a near complete hydrolyzation of formaldehyde, whereas formamide and urea remain intact in the solution. The analysis is further supported by density functional theory (DFT) calculations, showing a C 1s chemical shift of approximately 1.0 eV between hydrolyzed and nonhydrolyzed forms, which would give distinguishable features in the photoemission spectrum, if coexisting forms were present in the solutions.},
  author       = {Ottosson, Niklas and Aziz, Emad F and Bergersen, Henrik and Pokapanich, Wandared and Öhrwall, Gunnar and Svensson, Svante and Eberhardt, Wolfgang and Björneholm, Olle},
  issn         = {1520-5207},
  language     = {eng},
  number       = {51},
  pages        = {16642--16646},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Electronic Rearrangement upon the Hydrolyzation of Aqueous Formaldehyde Studied by Core-Electron Spectroscopies.},
  url          = {http://dx.doi.org/10.1021/jp806210m},
  volume       = {112},
  year         = {2008},
}