Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface

Daniel P. Miller, James Hooper, Scott Simpson, Paulo S. Costa, Nina Tymińska, Shannon M. McDonnell, Jason A. Bennett, Axel Enders, Eva Zurek

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Abstract

Systematic density functional theory calculations that treat the strong on-site 3d electron-electron interactions on iron via a Hubbard Ueff = 3.0 eV and the van der Waals (vdW) interactions between the substrate and adsorbate within the vdW-DF framework are employed to study the adsorption of the iron porphyrin (FeP) molecule to the Pt(111) surface. The more accurate vdW-DF-optPBE and vdW-DF-optB88 functionals found the same binding site to be the most stable and yielded binding energies that were within ∼20% of each other, whereas the binding energies computed with the vdW-DF-revPBE functional were substantially weaker. This work highlights the importance of vdW interactions for organometallic molecules chemisorbed to transition metal surfaces. The stability of the binding sites was found to depend upon the number of Fe-Pt and C-Pt bonds that were formed. Whereas in the gas phase the most stable spin state of FeP is the intermediate spin S = 1 state, the high spin S = 2 state is preferred for the FeP-Pt(111) system on the binding sites considered herein. The spin switch results from the elongation of the Fe-N bonds that occur upon adsorption.

Original languageEnglish (US)
Pages (from-to)29173-29181
Number of pages9
JournalJournal of Physical Chemistry C
Volume120
Issue number51
DOIs
StatePublished - Dec 29 2016

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All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Miller, D. P., Hooper, J., Simpson, S., Costa, P. S., Tymińska, N., McDonnell, S. M., Bennett, J. A., Enders, A., & Zurek, E. (2016). Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface. Journal of Physical Chemistry C, 120(51), 29173-29181. https://doi.org/10.1021/acs.jpcc.6b09408