The interplay between strong correlation and adsorption distances

Abstract

Adsorbed transition metal atoms can have partially filled $d$- or $f$-shells due to strong on-site Coulomb interaction. Capturing all effects originating from electron correlation in such strongly correlated systems is a challenge for electronic structure methods. It requires a sufficiently accurate description of the atomistic structure (in particular bond distances and angles), which is usually obtained from Kohn-Sham density functional theory (DFT), which due to the approximate nature of the exchange-correlation functional may provide an unreliable description of strongly correlated systems. To elucidate the consequences of this popular procedure, we apply a combination of DFT with the Anderson impurity model (AIM), as well as DFT+U for a calculation of the potential energy surface along the Co/Cu(001) adsorption coordinate, and compare the results with those obtained from DFT. The adsorption minimum is shifted towards larger distances by applying DFT+AIM, or the much cheaper DFT+U method, compared to the corresponding spin-polarized DFT results, by a magnitude comparable to variations between different approximate exchange-correlation functionals (0.08 to 0.12 Angstrom). This shift originates from an increasing correlation energy at larger adsorption distances, which can be traced back to the Co 3$d_{xy}$ and 3$d_{z2}$ orbitals being more correlated as the adsorption distance is increased.

References in corpus (14)

• A More Accurate Generalized Gradient Approximation for Solids
• Complexity in Strongly Correlated Electronic Systems
• Continuous-time Monte Carlo methods for quantum impurity models
• Ab initio calculations of quasiparticle band structure in correlated systems: LDA++ approach
• Ab-initio theory of superconductivity - I: Density functional formalism and approximate functionals
• Ab-initio theory of superconductivity - II: Applications to elemental metals
• Exact double-counting in combining the Dynamical Mean Field Theory and the Density Functional Theory
• Plane-wave based electronic structure calculations for correlated materials using dynamical mean-field theory and projected local orbitals
• Kondo temperature of magnetic impurities at surfaces
• A Self-consistent DFT+DMFT scheme in the Projector Augmented Wave : Applications to Cerium, Ce2O3 and Pu2O3 with the Hubbard I solver and comparison to DFT+U
• Multi-orbital Kondo physics of Co in Cu hosts
• Towards a full ab initio theory of strong electronic correlations in nanoscale devices
• Effect of electron correlations on the electronic structure and phase stability of FeSe upon lattice expansion
• Co adatoms on Cu surfaces: ballistic conductance and Kondo temperature

Cited by in corpus (3)

• State- and superstate-sampling in hybridization-expansion continuous-time quantum Monte Carlo
• Kondo screening in Co adatoms with full Coulomb interaction
• Co(CO)n/Cu(001): Towards understanding chemical control of the Kondo effect