Termination of the W 2 O y - + H 2 O/ D 2 O→ W 2 O y+1 - + H 2 / D 2 sequential oxidation reaction: An exploration of kinetic versus thermodynamic effects

David W. Rothgeb, Ekram Hossain, Nicholas J. Mayhall, Krishnan Raghavachari, Caroline Chick Jarrold

Research output: Contribution to journalArticle

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Abstract

Several mechanisms proposed and calculated for the sequential oxidation of tungsten suboxide clusters by H 2 O/ D 2 O [Mayhall, J. Chem. Phys. 131, 144302 (2009)] are evaluated using anion photoelectron spectroscopy of an apparent intermediate, W 2 O 6 D 2 -. The spectrum of W 2 O 6 D 2 -is consistent with the W 2 O 5 - + D 2 O→ W 2 O 6 - + D 2 intermediate in which the initial water addition involves the interaction of the oxygen from D 2 O with a tungsten atom, approaching from a direction with the least repulsion from the W 2 O 5 - oxygen atoms, coupled with the interaction between a deuterium with a tungsten-tungsten bridging oxygen on the cluster. The presence of W 2 O 6 H 2 - and W 2 O 6 D 2 - suggests that there is insufficient internal energy in the complex to surmount the barrier for rearrangement required for tungsten hydride and hydroxide formation necessary for H 2 or D 2 evolution, which was calculated to be energetically favorable. The quality of the calculations is verified by direct comparison between experimental photoelectron spectra of W 2 O 5 - and W 2 O 6 - and spectral simulations generated from the lowest energy structures calculated for W 2 O 5 -, W 2 O 6 - and their corresponding neutrals. The results shed light on the importance of repulsion on the pathway a reaction follows under room temperature conditions.

Original languageEnglish (US)
Article number144306
JournalJournal of Chemical Physics
Volume131
Issue number14
DOIs
StatePublished - 2009
Externally publishedYes

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Tungsten
tungsten
Thermodynamics
Oxidation
thermodynamics
oxidation
Kinetics
kinetics
Oxygen
Atoms
Deuterium
oxygen
Photoelectron spectroscopy
Photoelectrons
internal energy
Hydrides
hydroxides
hydrides
Anions
deuterium

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Termination of the W 2 O y - + H 2 O/ D 2 O→ W 2 O y+1 - + H 2 / D 2 sequential oxidation reaction : An exploration of kinetic versus thermodynamic effects. / Rothgeb, David W.; Hossain, Ekram; Mayhall, Nicholas J.; Raghavachari, Krishnan; Jarrold, Caroline Chick.

In: Journal of Chemical Physics, Vol. 131, No. 14, 144306, 2009.

Research output: Contribution to journalArticle

Rothgeb, David W. ; Hossain, Ekram ; Mayhall, Nicholas J. ; Raghavachari, Krishnan ; Jarrold, Caroline Chick. / Termination of the W 2 O y - + H 2 O/ D 2 O→ W 2 O y+1 - + H 2 / D 2 sequential oxidation reaction : An exploration of kinetic versus thermodynamic effects. In: Journal of Chemical Physics. 2009 ; Vol. 131, No. 14.
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abstract = "Several mechanisms proposed and calculated for the sequential oxidation of tungsten suboxide clusters by H 2 O/ D 2 O [Mayhall, J. Chem. Phys. 131, 144302 (2009)] are evaluated using anion photoelectron spectroscopy of an apparent intermediate, W 2 O 6 D 2 -. The spectrum of W 2 O 6 D 2 -is consistent with the W 2 O 5 - + D 2 O→ W 2 O 6 - + D 2 intermediate in which the initial water addition involves the interaction of the oxygen from D 2 O with a tungsten atom, approaching from a direction with the least repulsion from the W 2 O 5 - oxygen atoms, coupled with the interaction between a deuterium with a tungsten-tungsten bridging oxygen on the cluster. The presence of W 2 O 6 H 2 - and W 2 O 6 D 2 - suggests that there is insufficient internal energy in the complex to surmount the barrier for rearrangement required for tungsten hydride and hydroxide formation necessary for H 2 or D 2 evolution, which was calculated to be energetically favorable. The quality of the calculations is verified by direct comparison between experimental photoelectron spectra of W 2 O 5 - and W 2 O 6 - and spectral simulations generated from the lowest energy structures calculated for W 2 O 5 -, W 2 O 6 - and their corresponding neutrals. The results shed light on the importance of repulsion on the pathway a reaction follows under room temperature conditions.",
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