Termination of the W{sub 2}O{sub y}{sup -}+H{sub 2}O/D{sub 2}O{yields}W{sub 2}O{sub y+1}{sup -}+H{sub 2}/D{sub 2} sequential oxidation reaction: An exploration of kinetic versus thermodynamic effects

Journal Article · Wed Oct 14 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3246833· OSTI ID:21559790

Rothgeb, David W; Hossain, Ekram; Mayhall, Nicholas J; Raghavachari, Krishnan; Jarrold, Caroline Chick ^[1]

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1. Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405 (United States)

Several mechanisms proposed and calculated for the sequential oxidation of tungsten suboxide clusters by H{sub 2}O/D{sub 2}O[Mayhall et al., J. Chem. Phys. 131, 144302 (2009)] are evaluated using anion photoelectron spectroscopy of an apparent intermediate, W{sub 2}O{sub 6}D{sub 2}{sup -}. The spectrum of W{sub 2}O{sub 6}D{sub 2}{sup -} is consistent with the W{sub 2}O{sub 5}{sup -}+D{sub 2}O{yields}W{sub 2}O{sub 6}{sup -}+D{sub 2} intermediate in which the initial water addition involves the interaction of the oxygen from D{sub 2}O with a tungsten atom, approaching from a direction with the least repulsion from the W{sub 2}O{sub 5}{sup -} oxygen atoms, coupled with the interaction between a deuterium with a tungsten-tungsten bridging oxygen on the cluster. The presence of W{sub 2}O{sub 6}H{sub 2}{sup -} and W{sub 2}O{sub 6}D{sub 2}{sup -} 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{sub 2} or D{sub 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{sub 2}O{sub 5}{sup -} and W{sub 2}O{sub 6}{sup -} and spectral simulations generated from the lowest energy structures calculated for W{sub 2}O{sub 5}{sup -}, W{sub 2}O{sub 6}{sup -} and their corresponding neutrals. The results shed light on the importance of repulsion on the pathway a reaction follows under room temperature conditions.

• OSTI ID: 21559790
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 14; Other Information: DOI: 10.1063/1.3246833; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANIONS
ATOMS
COMPARATIVE EVALUATIONS
DEUTERIUM
HEAVY WATER
HYDROGEN
HYDROXIDES
INTERACTIONS
ION-MOLECULE COLLISIONS
ISOMERIZATION
MOLECULES
OXIDATION
OXYGEN
PHOTOELECTRON SPECTROSCOPY
REACTION KINETICS
SIMULATION
TUNGSTEN
TUNGSTEN HYDRIDES
VISIBLE RADIATION
CHARGED PARTICLES
CHEMICAL REACTIONS
COLLISIONS
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELECTRON SPECTROSCOPY
ELEMENTS
EVALUATION
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
ION COLLISIONS
IONS
ISOTOPES
KINETICS
LIGHT NUCLEI
METALS
MOLECULE COLLISIONS
NONMETALS
NUCLEI
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
RADIATIONS
REFRACTORY METAL COMPOUNDS
REFRACTORY METALS
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
TUNGSTEN COMPOUNDS
WATER