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

doi:10.1021/acs.jpcc.6b09408

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

School of Science (Behrend)

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

Systematic density functional theory calculations that treat the strong on-site 3d electron-electron interactions on iron via a Hubbard U_eff = 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 language	English (US)
Pages (from-to)	29173-29181
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	51
DOIs	https://doi.org/10.1021/acs.jpcc.6b09408
State	Published - Dec 29 2016

All Science Journal Classification (ASJC) codes

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

Access to Document

10.1021/acs.jpcc.6b09408

Cite this

@article{98816576607444ceb236c41517c0b39f,

title = "Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface",

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.",

author = "Miller, {Daniel P.} and James Hooper and Scott Simpson and Costa, {Paulo S.} and Nina Tymi{\'n}ska and McDonnell, {Shannon M.} and Bennett, {Jason A.} and Axel Enders and Eva Zurek",

note = "Funding Information: J.B. thanks the National Science Foundation (CHE-1305660) for financial support. Support from the Center of Computational Research at the University at Buffalo is acknowledged. E.Z. thanks the Alfred P. Sloan Foundation for a Research Fellowship (2013-2015). Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "29",

doi = "10.1021/acs.jpcc.6b09408",

language = "English (US)",

volume = "120",

pages = "29173--29181",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "51",

}

TY - JOUR

T1 - Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface

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

N1 - Funding Information: J.B. thanks the National Science Foundation (CHE-1305660) for financial support. Support from the Center of Computational Research at the University at Buffalo is acknowledged. E.Z. thanks the Alfred P. Sloan Foundation for a Research Fellowship (2013-2015). Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/12/29

Y1 - 2016/12/29

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85027246261&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027246261&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.6b09408

DO - 10.1021/acs.jpcc.6b09408

M3 - Article

AN - SCOPUS:85027246261

SN - 1932-7447

VL - 120

SP - 29173

EP - 29181

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 51

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this