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

Research output: Contribution to journalArticle

6 Citations (Scopus)

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

Fingerprint

deuterium fluorides
Porphyrins
Binding sites
porphyrins
Electronic structure
Iron
Binding Sites
electronic structure
Binding energy
iron
Electron-electron interactions
Adsorption
Molecules
binding energy
Organometallics
Adsorbates
adsorption
Transition metals
Density functional theory
Elongation

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., ... 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
Miller, Daniel P. ; Hooper, James ; Simpson, Scott ; Costa, Paulo S. ; Tymińska, Nina ; McDonnell, Shannon M. ; Bennett, Jason A. ; Enders, Axel ; Zurek, Eva. / Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 51. pp. 29173-29181.
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Miller, DP, Hooper, J, Simpson, S, Costa, PS, Tymińska, N, McDonnell, SM, Bennett, JA, Enders, A & Zurek, E 2016, 'Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface', Journal of Physical Chemistry C, vol. 120, no. 51, pp. 29173-29181. https://doi.org/10.1021/acs.jpcc.6b09408

Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface. / Miller, Daniel P.; Hooper, James; Simpson, Scott; Costa, Paulo S.; Tymińska, Nina; McDonnell, Shannon M.; Bennett, Jason A.; Enders, Axel; Zurek, Eva.

In: Journal of Physical Chemistry C, Vol. 120, No. 51, 29.12.2016, p. 29173-29181.

Research output: Contribution to journalArticle

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AU - Miller, Daniel P.

AU - Hooper, James

AU - Simpson, Scott

AU - Costa, Paulo S.

AU - Tymińska, Nina

AU - McDonnell, Shannon M.

AU - Bennett, Jason A.

AU - Enders, Axel

AU - Zurek, Eva

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Miller DP, Hooper J, Simpson S, Costa PS, Tymińska N, McDonnell SM et al. Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface. Journal of Physical Chemistry C. 2016 Dec 29;120(51):29173-29181. https://doi.org/10.1021/acs.jpcc.6b09408