Density Functional Theory and DFT+U Study of Transition Metal Porphines Adsorbed on Au(111) Surfaces and Effects of Applied Electric Fields.
We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 11; pp. 3659 - 3669 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
3/22/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=20426149&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 20426149 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 3/22/2006 vid: 128 iid: 11 pid: 997 pub: American Chemical Society artinfo: ui: 20426149 10.1021/ja056630o ppf: 3659 ppct: 10 formats: tig: atl: Density Functional Theory and DFT+U Study of Transition Metal Porphines Adsorbed on Au(111) Surfaces and Effects of Applied Electric Fields. aug: au: Leung, Kevin Rempe, Susan B. Schultz, Peter A. Sproviero, Eduardo M. Batista, Victor S. Chandross, Michael E. Medfortht, Craig J. affil: Sandia National Laboratories, MS 14/5, 1/10, 03/0, 1411, & 1349, Albuquerque, New Mexico 87185 Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107 su: Transition metals Density functionals Gold Electric fields Porphyrins Palladium sug: subj: Transition metals Density functionals Gold Electric fields Porphyrins Palladium ab: We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an electronvolt. The DFT+U technique, parametrized to B3LYP-predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than that of PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP and ∼0.1 Å changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first-row transition metal ion complexes in a condensed-matter setting. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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