Simple relationship between oxidation state and electron affinity in gas-phase metal-oxo complexes
Sarah E Waller1, Manisha Ray, Bruce L Yoder
1Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
The Journal of Physical Chemistry. A
|October 31, 2013
Summary
The electron affinities of tungsten oxide complexes are influenced more by the metal
Area of Science:
- Inorganic Chemistry
- Physical Chemistry
- Computational Chemistry
Background:
- Previous studies examined photoelectron spectra of various metal-oxo complexes.
- Understanding electron affinities is crucial for predicting chemical reactivity.
Purpose of the Study:
- Investigate the electronic structures of WO3H and WO2F anion and neutral complexes.
- Analyze the factors influencing electron affinities in transition metal-oxo complexes.
Main Methods:
- Photoelectron spectroscopy was used to measure electron affinities.
- Density Functional Theory (DFT) calculations with the B3LYP method were employed.
- Electronic structures and geometries of anions and neutrals were modeled.
Main Results:
- WO3H(-) and WO2F(-) exhibit comparable electron affinities to AlWO3(-).
- Electron affinity correlates with the +5 oxidation state of the transition metal center.
- Metal oxidation state appears more influential than closed-shell configurations on electron affinity.
Conclusions:
- The oxidation state of the metal atom is a primary driver of electron affinity in these systems.
- DFT calculations suggest pyramidal neutrals and planar anions, with low inversion barriers.
- Simple Franck-Condon simulations require adjustments to account for inversion effects.
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