A coverage dependent study of the adsorption of pyridine on the (111) coinage metal surfaces

Malone, Walter; Kara, Abdelkader

doi:10.1016/j.susc.2019.121525

A coverage dependent study of the adsorption of pyridine on the (111) coinage metal surfaces

Journal Article · Fri Nov 01 00:00:00 EDT 2019 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2019.121525· OSTI ID:1801753

Malone, Walter ^[1]; Kara, Abdelkader ^[2]

University of Central Florida, Orlando, FL (United States); OSTI
University of Central Florida, Orlando, FL (United States)

Using density functional theory we explore the adsorption of pyridine (NC₅H₅) on Cu, Ag, and Au(111) surfaces. To study the effect of coverage we run calculations on a 3 × 4 (12 atom), 4 × 4 (16 atom), 5 × 4 (20 atom), and 4 × 6 (24 atom) surface. To examine the role of the van der Waals interaction we use the following vdW inclusive functionals: optB86-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, rPW86-vdW2, SCAN+rVV10 along with the PBE functional. Regardless of functional, metal, and coverage we find the most energetically stable adsorption site to be a vertical site with the pyridine's N atom directly above a metal atom, which contradicts the available experimental literature. Introducing the vdW interaction lowers the energy gap between the most energetically favorable flat and vertical adsorption configurations. Moving to a higher coverage increases the overall interaction of the pyridine molecule with the surface. We also find that the SCAN+rVV10 functional performs similarly to the optB86b-vdW and optB88-vdW functional. Along with the geometric properties of the substrate/adsorbate system, here we report several electronic properties of the substrate/adsorbate system such as charge transfer from the surface to the molecule, change in the surface's work function, and change in d-band of the atoms in the first layer of the substrate.

View Accepted Manuscript (DOE)

Research Organization:: University of Central Florida, Orlando, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0007045; SC0007045

OSTI ID:: 1801753

Alternate ID(s):: OSTI ID: 1776223

Journal Information:: Surface Science, Journal Name: Surface Science Journal Issue: C Vol. 693; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
SCAN+rVV10
Van der Waals interaction
coinage metal surfaces
density functional theory
pyridine

A coverage dependent study of the adsorption of pyridine on the (111) coinage metal surfaces

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