Anion photoelectron spectroscopy and density functional investigation of vanadium carbide clusters

Kenneth Knappenberger, C. E. Jones, M. A. Sobhy, I. Iordanov, Jorge Osvaldo Sofo, A. W. Castleman

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

The influence of source conditions on vanadium-carbon cluster formation in a methane-vanadium plasma is explored and analyzed by photoelectron spectroscopy, revealing that the metal-carbon ratio has substantial influence over the cluster products. Experiments that employ large methane content produce carbon-rich mono- and divanadium carbides. The carbon-rich clusters show a preference for the formation of cyclic neutral and linear ionic structures. When the methane concentration is decreased, VmCn clusters are formed with m = 1-4 and n = 2-8. The photoelectron spectra of clusters formed under these conditions are indicative of a three-dimensional network. We have measured a significantly lower vertical electron affinity for the VC 2, V2C3, and V4C6 clusters compared with proximate species. Interestingly, the VC2 species is a proposed building block of the M8C12 Met-Car cluster, and the 2,3 and 4,6 clusters correspond to the 1/4 and 1/2 Met-Car cages, respectively. This correlation is taken as evidence of their importance in the formation of the larger Met-Car species. These results are supported by density functional theory (DFT) calculations carried out at the PBE/GGA level.

Original languageEnglish (US)
Pages (from-to)12814-12821
Number of pages8
JournalJournal of Physical Chemistry A
Volume110
Issue number47
DOIs
StatePublished - Nov 30 2006

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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