Above the Kondo temperature, the Kohn-Sham zero-bias conductance of an Anderson junction has been shown to completely miss the Coulomb blockade. Within a standard model for the spectral function, we deduce a parameterization for both the onsite excha
nge-correlation potential and the bias drop as a function of the site occupation that applies for all correlation strengths. We use our results to sow doubt on the common interpretation of such corrections as arising from dynamical exchange-correlation contributions.
The electronic structure of organic-inorganic interfaces often feature resonances originating from discrete molecular orbitals coupled to continuum lead states. An example are molecular junctions, individual molecules bridging electrodes, where the s
hape and peak energy of such resonances dictate junction conductance, thermopower, I-V characteristics and related transport properties. In molecular junctions where off-resonance coherent tunneling dominates transport, resonance peaks in the transmission function are often assumed to be Lorentzian functions with an energy-independent broadening parameter $Gamma$. Here we define a new energy-dependent resonance broadening function, $Gamma(E)$, based on diagonalization of non-Hermitian matrices, which can describe resonances of a more complex, non-Lorentzian nature and can be decomposed into components associated with the left and right lead, respectively. We compute this quantity via an emph{ab initio} non-equilibrium Greens function approach based on density functional theory for both symmetric and asymmetric molecular junctions, and show that our definition of $Gamma(E)$, when combined with Breit-Wigner formula, reproduces the transmission calculated from DFT-NEGF. Through a series of examples, we illustrate how this approach can shed new light on experiments and understanding of junction transport properties in terms of molecular orbitals.
The exact ground-state exchange-correlation functional of Kohn-Sham density functional theory yields the exact transmission through an Anderson junction at zero bias and temperature. The exact impurity charge susceptibility is used to construct the e
xact exchange-correlation potential. We analyze the successes and limitations of various types of approximations, including smooth and discontinuous functionals of the occupation, as well as symmetry-broken approaches.
Modern density functional theory (DFT) calculations employ the Kohn-Sham (KS) system of non-interacting electrons as a reference, with all complications buried in the exchange-correlation energy (Exc). The adiabatic connection formula gives an exact
expression for Exc. We consider DFT calculations that instead employ a reference of strictly-correlated electrons. We define a decorrelation energy that relates this reference to the real system, and derive the corresponding adiabatic connection formula. We illustrate this theory in three situations, namely the uniform electron gas, Hookes atom, and the stretched hydrogen molecule. The adiabatic connection for strictly-correlated electrons provides an alternative perspective for understanding density functional theory and constructing approximate functionals.
In density functional theory (DFT), the exchange-correlation functional can be exactly expressed by the adiabatic connection integral. It has been noticed that as lambda goes to infinity, the lambda^(-1) term in the expansion of W(lambda) vanishes. W
e provide a simple but rigorous derivation to this exact condition in this work. We propose a simple parametric form for the integrand, satisfying this condition, and show that it is highly accurate for weakly-correlated two-electron systems.
