On the asymmetry in molybdenum–oxygen bonding in the MoO3 structure: ETS–NOCV analysisReport as inadecuate

On the asymmetry in molybdenum–oxygen bonding in the MoO3 structure: ETS–NOCV analysis - Download this document for free, or read online. Document in PDF available to download.

Structural Chemistry

, Volume 23, Issue 5, pp 1369–1375

First Online: 04 June 2012Received: 14 July 2011Accepted: 17 March 2012


In the present study, the analysis of natural orbitals for chemical valence NOCV combined with the extended-transition-state ETS bond-energy decomposition method ETS–NOCV was applied to characterize an asymmetry in Mo–O bonding in MoO3 crystal. Considered were three non-equivalent oxygen sites O1, O2, O3 in the Mo7O30H18 cluster model of 010 surface of MoO3. The ETS–NOCV method leads to the conclusion that an increase in the Mo–O distances, from 1.68 Å for Mo–O1, through 1.73 Å for Mo–O2, up to 1.94 Å for Mo–O3, is directly related to decrease in strength of both σ- and π-contributions of Mo–O bond. Further, Mo–O connection appeared to exhibit both ionic the charge transfer from 2p orbital of oxygen to molybdenum and the covalent charge accumulation in the region of Mo–O components. Finally, the trend in the orbital energy stabilization ΔEorb originating from the dominant σ- and π-bond contributions appeared to correlate very well with the oxygen-vacancy formation energies published earlier by Tokarz-Sobieraj et al. Surf Sci 489:107, 2001.

KeywordsMolybdenum oxide Charge and energy decomposition ETS-NOCV NOCV-deformation density contributions This article is dedicated to Prof. Małgorzata Witko.

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Author: Mariusz P. Mitoraj - Artur Michalak

Source: https://link.springer.com/

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