Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces

  title={Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces},
  author={A. M. C. Souza and Ivan Rungger and Chaitanya Das Pemmaraju and Udo Schwingenschloegl and Stefano Sanvito},
  journal={Physical Review B},
We present a computational scheme for extracting the energy-level alignment of a metal/molecule interface, based on constrained density functional theory and local exchange and correlation functionals. The method, appliedheretobenzeneonLi(100),allowsustoevaluatecharge-transferenergies,aswellasthespatialdistribution of the image charge induced on the metal surface. We systematically study the energies for charge transfer from the molecule to the substrate as function of the molecule-substrate… 

Figures and Tables from this paper

Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory
This paper develops and applies an efficient theoretical method, based on density functional theory (DFT), that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces and shows that the method correctly captures level alignment trends across chemical systems.
Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional
The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in
Semiempirical modeling of electrochemical charge transfer.
The variation of E°' with the structure of the Ag20-pyridine system is only weakly correlated with changes in either the ground-state interaction energy or the charge-transfer excited-state energies at zero applied potential, which shows the importance of calculations that include an applied potential in determining the variation of formal potential with geometry.
A simplified density functional theory method for investigating charged adsorbates on an ultrathin, insulating film supported by a metal substrate.
  • I. Scivetti, M. Persson
  • Physics
    Journal of physics. Condensed matter : an Institute of Physics journal
  • 2014
This new DFT-PC-FF method allows us to handle different charge states of adsorbates in a controlled and accurate manner with a considerable reduction of the computational time, and it is now possible to calculate vertical transition and reorganization energies for the charging and discharging of Adsorbates that cannot be obtained by current DFT methodologies that include the metal substrate.
The energy level alignment at metal–molecule interfaces using Wannier–Koopmans method
We apply a recently developed Wannier–Koopmans method (WKM), based on density functional theory (DFT), to calculate the electronic energy level alignment at an interface between a molecule and metal
The image charge effect and vibron-assisted processes in Coulomb blockade transport: a first principles approach.
It is demonstrated that energy level renormalization due to the image charge effect is crucial to the prediction of the current onset in the current-voltage, I-V, curves as a function of electrode separation.
Transition-Based Constrained DFT for the Robust and Reliable Treatment of Excitations in Supramolecular Systems
Despite the variety of available computational approaches, state-of-the-art methods for calculating excitation energies, such as time-dependent density functional theory (TDDFT), are computationally
Implementation of Constrained DFT for Computing Charge Transfer Rates within the Projector Augmented Wave Method.
A general and robust implementation of cDFT within the projector augmented wave (PAW) framework, which produces qualitatively and quantitatively accurate results when benchmarked against self-interaction corrected DFT and high-level CCSD(T) calculations at a fraction of the computational cost.
Transport gap renormalization at a metal-molecule interface using DFT-NEGF and spin unrestricted calculations.
A fully self-consistent scissor operator is implemented to correct the highest occupied molecular orbital-lowest unoccupied molecular orbital gap in transport calculations for single molecule junctions.
Predicting the conductance of strongly correlated molecules: the Kondo effect in perchlorotriphenylmethyl/Au junctions.
A method that combines density functional theory, quantum transport theory, numerical renormalization group (NRG) calculations and renormalized super-perturbation theory (rSPT) to compute both equilibrium and non-equilibrium properties of strongly correlated nanoscale systems at low temperatures effectively from first principles is developed.