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Published January 14, 2021 | Supplemental Material + In Press
Journal Article Open

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

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.

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.

Attached Files

Supplemental Material - jz0c03126_si_001.txt

Supplemental Material - jz0c03126_si_002.pdf

Supplemental Material - jz0c03126_si_003.txt

In Press - 1404-JPCL-Hao_LG-vdW.pdf

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Additional details

Created:
August 20, 2023
Modified:
October 23, 2023