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 (HAuPH3)2 aurophilic complex. Binding energies are computed for Au4 interacting with the following ligands: SCN(-), benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

“…Increasing the total fraction of HF exchange too much may distort the balance in error compensation between correlation and exchange functionals, resulting in the incorrect behavior of the energy contributions. 89,90 We show this by plotting the first-order, E (1) = E elst + E exch , and dispersion, E (2) disp,tot = E (2) exch−disp + E (2) disp energies, for the Ar. .…”

Experimental and theoretical electronic structure of quinacridone

“…This is not surprising: similar observations were made by Refaely-Abramson et al 38 and confirmed in additional studies. 39,92,93 In order to provide an explanation for the origin of this behavior, orbital plots of the five highest-occupied orbitals, as well as the LUMO, are shown in Fig. 2b.…”

Noncovalent interactions determine the conformation of aurophilic complexes with 2-mercapto-4-methyl-5-thiazoleacetic acid ligands

“…These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_ request/cif. (19) C11-S11-Au1 104.6(3) C31-S31-Au2 103.2(3) Au1-S2-C1-S1 −3.6(4) Au1-S1-C1-S2…”

“…12,13 Finally, over the last decade the role of gold thiolates in the formation and stabilization of nanoparticles has also been a matter of extensive studies. 12,[14][15][16][17][18][19] Gold bisthiolato complexes constitute an interesting group of thiolates. In this class of compounds the Au(I) centre may be incorporated either in the cationic or anionic units of the [Au(SR) 2 ] +/− type depending on the nature of the ligand.…”