O2 on Ag(110): A puzzle for exchange-correlation functionals

An important part of condensed matter physics in recent years has involved detailed study of inelastic interactions between swift electrons and condensed matter surfaces. Here we will review some aspects of such interactions.Surface excitations have long been recognized as dominant in determining the exchange-correlation energy of charged particles outside the surface. Properties of surface and bulk polaritons, plasmons and optical phonons in plane-bounded and spherical systems will be discussed from the viewpoint of semiclassical and quantal dielectric theory. Plasmons at interfaces between dissimilar dielectrics and in superlattice configurations will also be considered.

Download Full-text

Exchange-Correlation Energy Densities and Response Potentials: Connection Between Two Definitions and Analytical Model for the Strong-Coupling Limit of a Stretched Bond

10.26434/chemrxiv.10283678.v1 ◽

2019 ◽

Author(s):

S. Giarrusso ◽

Paola Gori-Giorgi

Keyword(s):

Density Functional Theory ◽

Strong Coupling ◽

Density Functional ◽

Correlation Energy ◽

Order Term ◽

Strong Coupling Limit ◽

Local Form ◽

Coupling Constant ◽

Functional Theory ◽

Exchange Correlation

We analyze in depth two widely used definitions (from the theory of conditional probablity amplitudes and from the adiabatic connection formalism) of the exchange-correlation energy density and of the response potential of Kohn-Sham density functional theory. We introduce a local form of the coupling-constant-dependent Hohenberg-Kohn functional, showing that the difference between the two definitions is due to a corresponding local first-order term in the coupling constant, which disappears globally (when integrated over all space), but not locally. We also design an analytic representation for the response potential in the strong-coupling limit of density functional theory for a model single stretched bond.<br>

Download Full-text

Evaluating Transition Metal Barrier Heights with the Latest DFT Exchange–Correlation Functionals – the MOBH35 Benchmark Dataset

10.26434/chemrxiv.7732262.v1 ◽

2019 ◽

Author(s):

Mark Iron ◽

Trevor Janes

Keyword(s):

Transition Metal ◽

Density Functional ◽

Computational Cost ◽

Basis Set ◽

Functional Theory ◽

Exchange Correlation ◽

Barrier Heights ◽

Complete Basis Set ◽

Complete Basis Set Limit ◽

Hybrid Functionals

A new database of transition metal reaction barrier heights – MOBH35 – is presented. Benchmark energies (forward and reverse barriers and reaction energy) are calculated using DLPNO-CCSD(T) extrapolated to the complete basis set limit using a Weizmann1-like scheme. Using these benchmark energies, the performance of a wide selection of density functional theory (DFT) exchange–correlation functionals, including the latest from the Truhlar and Head-Gordon groups, is evaluated. It was found, using the def2-TZVPP basis set, that the ωB97M-V (MAD 1.8 kcal/mol), ωB97X-V (MAD 2.1 kcal/mol) and SCAN0 (MAD 2.1 kcal/mol) hybrid functionals are recommended. The double-hybrid functionals PWPB95 (MAD 1.6 kcal/mol) and B2K-PLYP (MAD 1.8 kcal/mol) did perform slightly better but this has to be balanced by their increased computational cost.

Download Full-text

Electronic Structure of Molecules, Surfaces, and Molecules on Surfaces with the Local Modified Becke–Johnson Exchange–Correlation Potential

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.1c00255 ◽

2021 ◽

Author(s):

Tomáš Rauch ◽

Miguel A. L. Marques ◽

Silvana Botti

Keyword(s):

Electronic Structure ◽

Exchange Correlation ◽

Exchange Correlation Potential ◽

Structure Of Molecules ◽

Correlation Potential

Download Full-text

Protein-ligand free energies of binding from full-protein DFT calculations: convergence and choice of exchange-correlation functional

Physical Chemistry Chemical Physics ◽

10.1039/d1cp00206f ◽

2021 ◽

Author(s):

Lennart Gundelach ◽

Christofer S Tautermann ◽

Thomas Fox ◽

Chris-Kriton Skylaris

Keyword(s):

Drug Discovery ◽

Ligand Binding ◽

Dft Calculations ◽

Quantum Mechanical ◽

Free Energies ◽

Ligand Interaction ◽

Exchange Correlation ◽

Ligand Free ◽

Protein Ligand Interaction ◽

Binding Free Energies

The accurate prediction of protein-ligand binding free energies with tractable computational methods has the potential to revolutionize drug discovery. Modeling the protein-ligand interaction at a quantum mechanical level, instead of...

Download Full-text