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Title: Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces

Abstract

We explore the adsorption of pyridine on Cu, Ag, Au, and Pt(110) surfaces using density functional theory. To account for the van der Waals interaction, we use the optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2 functionals. For comparison, we also run calculations using the generalized gradient approximation-PBE (Perdew–Burke–Ernzerhof) functional. We find the most stable adsorption site to depend on both metal and functional, with two energetically favorable adsorption sites, namely, a vertically oriented site and a flat pyridine site. We calculate that every functional predicts pyridine to lie in the vertical configuration on the coinage metals at a low coverage. On Pt(110), by contrast, we calculate all the functionals—except rPW86-vdW2—to predict pyridine to lie flat at a low coverage. By analyzing these differences for these adsorption configurations, along with various geometric and electronic properties of the adsorbate/substrate system, we access in detail the performance of the 6 functionals we use. We also characterize the nature of the bonding of pyridine on the coinage metals from weak to strong physisorption, depending on the functional used. On Pt(110), we characterize the nature of the bonding of pyridine as ranging from strong physisorption to strong chemisorption depending again on the functional used, illustrating bothmore » the importance of the van der Waals interaction to this system and that this system can make a stringent test for computational methods.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Central Florida, Orlando, FL (United States). Physics Dept.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of Central Florida, Orlando, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543890
Grant/Contract Number:  
SC0007045
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Malone, Walter, von der Heyde, Johnathan, and Kara, Abdelkader. Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces. United States: N. p., 2018. Web. doi:10.1063/1.5054788.
Malone, Walter, von der Heyde, Johnathan, & Kara, Abdelkader. Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces. United States. doi:10.1063/1.5054788.
Malone, Walter, von der Heyde, Johnathan, and Kara, Abdelkader. Tue . "Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces". United States. doi:10.1063/1.5054788. https://www.osti.gov/servlets/purl/1543890.
@article{osti_1543890,
title = {Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces},
author = {Malone, Walter and von der Heyde, Johnathan and Kara, Abdelkader},
abstractNote = {We explore the adsorption of pyridine on Cu, Ag, Au, and Pt(110) surfaces using density functional theory. To account for the van der Waals interaction, we use the optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2 functionals. For comparison, we also run calculations using the generalized gradient approximation-PBE (Perdew–Burke–Ernzerhof) functional. We find the most stable adsorption site to depend on both metal and functional, with two energetically favorable adsorption sites, namely, a vertically oriented site and a flat pyridine site. We calculate that every functional predicts pyridine to lie in the vertical configuration on the coinage metals at a low coverage. On Pt(110), by contrast, we calculate all the functionals—except rPW86-vdW2—to predict pyridine to lie flat at a low coverage. By analyzing these differences for these adsorption configurations, along with various geometric and electronic properties of the adsorbate/substrate system, we access in detail the performance of the 6 functionals we use. We also characterize the nature of the bonding of pyridine on the coinage metals from weak to strong physisorption, depending on the functional used. On Pt(110), we characterize the nature of the bonding of pyridine as ranging from strong physisorption to strong chemisorption depending again on the functional used, illustrating both the importance of the van der Waals interaction to this system and that this system can make a stringent test for computational methods.},
doi = {10.1063/1.5054788},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 21,
volume = 149,
place = {United States},
year = {2018},
month = {12}
}

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