Early- versus late-transition-metal-oxo bonds: The electronic structure of VO+ and RuO+

Emily A. Carter, William A. Goddard

Research output: Contribution to journalArticle

108 Scopus citations

Abstract

From all-electron ab initio generalized valence bond calculations (GVBCI-SCF) on VO+ and RuO+, we find that an accurate description of the bonding is obtained only when important resonance configurations are included self-consistently in the wave function. The ground state of VO+(3Σ-) has a triple bond similar to that of CO, with Decalcd(V-O) = 128.3 kcal/mol [Deexptl(V-O) = 1.31 ± 5 kcal/mol], while the ground state of RuO+(4Δ) has a double bond similar to that of O2, with Decalcd(Ru-O) = 67.1 kcal/mol. Vertical excitation energies for a number of low-lying electronic states of VO+ and RuO+ are also reported. These results indicate fundamental differences in the nature of the metal-oxo bond in early and late metal oxo complexes that explain the observed trends in reactivity (e.g., early metal oxides are thermodynamically stable whereas late metal oxo complexes are highly reactive oxidants). Finally, we have used these results to predict the ground states of MO+ for other first-row transition-metal oxides.

Original languageEnglish (US)
Pages (from-to)2109-2115
Number of pages7
JournalJournal of physical chemistry
Volume92
Issue number8
DOIs
StatePublished - Jan 1 1988
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Early- versus late-transition-metal-oxo bonds: The electronic structure of VO<sup>+</sup> and RuO<sup>+</sup>'. Together they form a unique fingerprint.

  • Cite this