Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

Journal Article · Thu Apr 28 04:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4947225· OSTI ID:22660872

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk ^[1]

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1. Interdisciplinary Nanoscience Center (iNANO), Department of Physics and Astronomy, Aarhus University, Aarhus (Denmark)

The adsorption, diffusion, and dissociation of pyridine, C{sub 5}H{sub 5}N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom. The origin of the diffusion pathway is discussed in terms of the C{sub 2}–Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).

• OSTI ID: 22660872
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
97 MATHEMATICS AND COMPUTING
ADSORPTION
COMPUTER CALCULATIONS
CRYSTALS
DENSITY FUNCTIONAL METHOD
DIFFUSION
DOUBLE BONDS
EXPERIMENTAL DATA
POTENTIAL ENERGY
PYRIDINE
REACTION HEAT
VAN DER WAALS FORCES