Surface Adsorption from the Exchange-Hole Dipole Moment Dispersion Model

Abstract

The accurate calculation of intermolecular interaction energies with density functional theory requires methods that include a treatment of long-range, nonlocal dispersion correlation. In this work, we explore the ability of the exchange-hole dipole moment (XDM) dispersion correction to model molecular surface adsorption. Adsorption energies are calculated for six small aromatic molecules (benzene, furan, pyridine, thiophene, thiophenol, and benzenediamine) and the four DNA nucleobases (adenine, thymine, guanine, and cytosine) on the (111) surfaces of the three coinage metals (copper, silver, and gold). For benzene, where the experimental reference data is most precise, the mean absolute error in the computed absorption energies is 0.04 eV. For the other aromatic molecules, the computed binding energies are found to be within 0.09 eV of the available reference data, on average, which is well below the expected experimental uncertainties for temperature-programmed desorption measurements. Unlike other dispersion-corrected functionals, adequate performance does not require changes to the canonical XDM implementation, and the good performance of XDM is explained in terms of the behavior of the exchange hole. Additionally, the base functional employed (B86bPBE) is also optimal for molecular studies, making B86bPBE-XDM an excellent candidate for studying chemistry on material surfaces. Finally, the noncovalent interaction (NCI) plot technique is shown to detect adsorption effects in real space on the order of tenths of an eV.

Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

“…In terms of modern practical methods to take on nanotechnology applications in which dispersion forces compete with chemical bonding, GGA density functionals are very promising when combined with dispersion methods like D3 132 (especially in its three-body corrected form D3(ABC) 133 ), the many-body dispersion method (MBD), 134,135 the Vydrov and van Voohris (VV10) method, 137 or the exchange-hole dipole model (XDM). 136 These approaches have also been shown to be successful for many other problems in surface chemistry, 20 including noncovalent binding involving graphene and van der Waals heterostructures. [159][160][161] Personally, we have applied the D3 correction to Au-S bonds using PW91 and obtained satisfactory results, 83,84 but we recommend combination with PBE instead as this method allows for a much cleaner separation of dispersion and covalent effects.…”

Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces

“…The SCAN+rVV10 is overbinding compared to the earlier results from PBE+vdW surf 68 and B86bPBE-XDM approximations 38 too. Comparison with the relevant results of Christian et al38 shows that B86bPBE-XDM results do not reflect the qualitative tendency that Cu and Au surfaces bind the thiophene about equally strongly and slightly stronger than Ag.…”

“…37 However, the estimated binding energies might display an uncertainty larger than the chemical accuracy of 0.04 eV required for an accurate description of the adsorption. 38 A considerably more accurate complete analysis method would lead to more accurate results, 37,38 but no such results are available for thiophene on coinage metal surfaces according to our knowledge. The nonlocal random phase approximation (RPA) 10,39 could be a reliable reference for long-range vdW interactions.…”

The Controversial Orientation of Adenine on Gold and Silver

“…Conversely, the computational studies discussed in Sections 2.2 and 2.4 have reported significantly different conclusions from each other . These discrepancies, at least for this field, highlight the importance of using computational tools to help interpret experimental measurements of physical phenomena, rather than relying on them exclusively.…”