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Title: Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts

Abstract

Donor-acceptor interactions are notoriously difficult and unpredictable for conventional density functional theory (DFT) methodologies. This work presents a reliable computational treatment of gold-ligand interactions of the donor-acceptor type within DFT. These interactions require a proper account of the ionization potential of the electron donor and electron affinity of the electron acceptor. This is accomplished in the Generalized Kohn Sham framework that allows one to relate these properties to the frontier orbitals in DFT via the tuning of range-separated functionals. A donor and an acceptor typically require different tuning schemes. This poses a problem when the binding energies are calculated using the supermolecular method. A two-parameter tuning for the monomer properties ensures that a common functional, optimal for both the donor and the acceptor, is found. A reliable DFT approach for these interactions also takes into account the dispersion contribution. The approach is validated using the water dimer and the (HAuPH{sub 3}){sub 2} aurophilic complex. Binding energies are computed for Au{sub 4} interacting with the following ligands: SCN{sup −}, benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.

Authors:
; ;  [1];  [1]
  1. Faculty of Chemistry, Warsaw University, Pasteura 1, 02-093 Warszawa (Poland)
Publication Date:
OSTI Identifier:
22311297
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 24; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; ANIONS; BINDING ENERGY; DENSITY FUNCTIONAL METHOD; ELECTRONS; GOLD; INTERACTIONS; LIGANDS; MONOMERS; PYRIDINE; WATER

Citation Formats

Koppen, Jessica V., Szczęśniak, Małgorzata M., E-mail: bryant@oakland.edu, Hapka, Michał, Modrzejewski, Marcin, Chałasiński, Grzegorz, and Department of Chemistry, Oakland University, Rochester, Michigan 48309. Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts. United States: N. p., 2014. Web. doi:10.1063/1.4885137.
Koppen, Jessica V., Szczęśniak, Małgorzata M., E-mail: bryant@oakland.edu, Hapka, Michał, Modrzejewski, Marcin, Chałasiński, Grzegorz, & Department of Chemistry, Oakland University, Rochester, Michigan 48309. Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts. United States. https://doi.org/10.1063/1.4885137
Koppen, Jessica V., Szczęśniak, Małgorzata M., E-mail: bryant@oakland.edu, Hapka, Michał, Modrzejewski, Marcin, Chałasiński, Grzegorz, and Department of Chemistry, Oakland University, Rochester, Michigan 48309. 2014. "Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts". United States. https://doi.org/10.1063/1.4885137.
@article{osti_22311297,
title = {Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts},
author = {Koppen, Jessica V. and Szczęśniak, Małgorzata M., E-mail: bryant@oakland.edu and Hapka, Michał and Modrzejewski, Marcin and Chałasiński, Grzegorz and Department of Chemistry, Oakland University, Rochester, Michigan 48309},
abstractNote = {Donor-acceptor interactions are notoriously difficult and unpredictable for conventional density functional theory (DFT) methodologies. This work presents a reliable computational treatment of gold-ligand interactions of the donor-acceptor type within DFT. These interactions require a proper account of the ionization potential of the electron donor and electron affinity of the electron acceptor. This is accomplished in the Generalized Kohn Sham framework that allows one to relate these properties to the frontier orbitals in DFT via the tuning of range-separated functionals. A donor and an acceptor typically require different tuning schemes. This poses a problem when the binding energies are calculated using the supermolecular method. A two-parameter tuning for the monomer properties ensures that a common functional, optimal for both the donor and the acceptor, is found. A reliable DFT approach for these interactions also takes into account the dispersion contribution. The approach is validated using the water dimer and the (HAuPH{sub 3}){sub 2} aurophilic complex. Binding energies are computed for Au{sub 4} interacting with the following ligands: SCN{sup −}, benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.},
doi = {10.1063/1.4885137},
url = {https://www.osti.gov/biblio/22311297}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 24,
volume = 140,
place = {United States},
year = {Sat Jun 28 00:00:00 EDT 2014},
month = {Sat Jun 28 00:00:00 EDT 2014}
}