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London Dispersion Corrections to Density Functional Theory for Transition Metals Based on Fitting to Experimental Temperature-Programmed Desorption of Benzene Monolayers

Yang, Hao and Cheng, Tao and Goddard, William A., III (2021) London Dispersion Corrections to Density Functional Theory for Transition Metals Based on Fitting to Experimental Temperature-Programmed Desorption of Benzene Monolayers. Journal of Physical Chemistry Letters, 12 (1). pp. 73-79. ISSN 1948-7185. https://resolver.caltech.edu/CaltechAUTHORS:20201215-141038032

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Abstract

Standard implementations of generalized gradient approximation (GGA)-based density functional theory (DFT) describe well strongly bound molecules and solids but fail to describe long-range London dispersion or van der Waals (vdW) attraction interactions that are important in molecular crystals and two-dimensional solids. To provide accurate values for the vdW distance and energies for the metals Cu, Ag, Au, Ni, Pd, and Pt, we determined empirical vdW corrections to Perdew, Burke, and Ernzerhof (PBE) DFT by fitting the experimental adsorption enthalpies measured by temperature-programmed desorption (TPD) from benzene monolayers by Campbell and co-workers ( J. Phys. Chem. C 2016, 120, 25161−25172). Benzene physisorbed to these metals without chemical reaction; therefore, we consider the bonding to be vdW. We use the low gradient form for the vdW corrections, E_(vdW-LG) = −C_(6LG)/[R⁶ + R_(vdwLG)⁶] with just two parameters per atom (C_(6LG) and R_(vdwLG)). This LG form leads to negligible changes in bond distances and angles, so adjusting the parameters should not sacrifice accuracy for the bonding interactions. We demonstrate that the parameters fitted to benzene also describe well the physisorption enthalpies for other hydrocarbons (naphthalene, cyclohexane, methane, ethane, and propane) on Pt. We also report low gradient vdW correction parameters for the noble gases that fit the equilibrium lattice parameter and heat of vaporization of the crystals.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.0c03126DOIArticle
ORCID:
AuthorORCID
Yang, Hao0000-0002-8241-6231
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2020 American Chemical Society. Received: October 14, 2020; Accepted: December 3, 2020; Published: December 11, 2020. T.C. and H.Y. thank the National Natural Science Foundation of China (21975148), the Natural Science Foundation of Jiangsu Higher Education Institutions (SBK20190810), the Jiangsu Province High-Level Talents (JNHB-106), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for financial support. H.Y. thanks China Postdoctoral Science Foundation (2019M660128) for financial support. This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology. W.A.G. received support from the US National Science Foundation (CBET-1805022 and CBET-2005250). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China21975148
Natural Science Foundation of Jiangsu Higher Education InstitutionsSBK20190810
Government of Jiangsu ProvinceJNHB-106
Priority Academic Program Development of Jiangsu Higher Education InstitutionsUNSPECIFIED
China Postdoctoral Science Foundation2019M660128
Collaborative Innovation Center of Suzhou Nano Science and TechnologyUNSPECIFIED
NSFCBET-1805022
NSFCBET-2005250
Subject Keywords:Crystals, Hydrocarbons, Aromatic compounds, Platinum,Energy
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1404
Issue or Number:1
Record Number:CaltechAUTHORS:20201215-141038032
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20201215-141038032
Official Citation:London Dispersion Corrections to Density Functional Theory for Transition Metals Based on Fitting to Experimental Temperature-Programmed Desorption of Benzene Monolayers. Hao Yang, Tao Cheng, and William A. Goddard. The Journal of Physical Chemistry Letters 2021 12 (1), 73-79; DOI: 10.1021/acs.jpclett.0c03126
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107100
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:15 Dec 2020 23:13
Last Modified:27 Mar 2021 07:24

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