First-principles investigation of transient current of molecular devices by using complex absorbing potential

Based on the non-equilibrium Green's function (NEGF) coupled with density function theory (DFT), namely, NEGF-DFT quantum transport theory, we propose an efficient formalism to calculate the transient current of molecular devices under a step-like pulse from first principles. By combining NEGF-DFT with the complex absorbing potential (CAP), the computational complexity of our formalism (NEGF-DFT-CAP) is proportional to $\emph{O}(N)$ where $N$ is the number of time steps in the time-dependent transient calculation. Compared with state-of-the-art algorithm of first principles time-dependent calculation that scales with at least $N^2$, this order N technique drastically reduces the computational burden making it possible to tackle realistic molecular devices. To ensure the accuracy of our method, we carry out the benchmark calculation compared with exact NEGF-TDDFT formalism and they agree well with each other. As an illustration, we investigate the transient current of molecular device Al-C$_3$-Al from first principles

Ab initio calculation of the binding energy of impurities in semiconductors: Application to Si nanowires

We discuss the binding energy E_b of impurities in semiconductors within density functional theory (DFT) and the GW approximation, focusing on donors in nanowires as an example. We show that DFT succeeds in the calculation of E_b from the Kohn-Sham (KS) hamiltonian of the ionized impurity, but fails in the calculation of E_b from the KS hamiltonian of the neutral impurity, as it misses most of the interaction of the bound electron with the surface polarization charges of the donor. We trace this deficiency back to the lack of screened exchange in the present functionals

Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the accuracy and stability of WFT-in-DFT embedding calculations. In particular, we develop spin-dependent embedding potentials in both restricted and unrestricted orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and we develop an orbital-occupation-freezing technique to improve the convergence of optimized effective potential (OEP) calculations that arise in the evaluation of the embedding potential. The new techniques are demonstrated in applications to the van-der-Waals-bound ethylene-propylene dimer and to the hexaaquairon(II) transition-metal cation. Calculation of the dissociation curve for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating errors in the dispersion interactions due to conventional exchange-correlation (XC) functionals while simultaneously avoiding errors due to subsystem partitioning across covalent bonds. Application of WFT-in-DFT embedding to the calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II) cation reveals that the majority of the dependence on the DFT XC functional can be eliminated by treating only the single transition-metal atom at the WFT level; furthermore, these calculations demonstrate the substantial effects of open-shell contributions to the embedding potential, and they suggest that restricted open-shell WFT-in-DFT embedding provides better accuracy than unrestricted open-shell WFT-in-DFT embedding due to the removal of spin contamination.Comment: 11 pages, 5 figures, 2 table

Density functional electronic spectrum of the CuO−6−10Cu O_{-6}^{-10} cluster and possible local Jahn-Teller distorsions in the La-Ba-Cu-O superconductor

We present a density functional theory (DFT) calculation in the generalized gradient approximation to study the possibility for the existence of Jahn-Teller (JT) or pseudo Jahn-Teller (PJT) type local distortions in the La-Ba-Cu-O superconducting system. We performed the calculation and correspondingly group theory classification of the electronic ground state of the CuO${_{6}}^{-10}$ elongated octahedra cluster, immersed in a background simulating the superconductor. Part of the motivation to do this study is that the origin of the apical deformation of the CuO${_{6}}^{-10}$ cluster is not due to a pure JT effect, having therefore a non {\it a priori} condition to remove the degeneracy of the electronic ground state of the parent regular octahedron. We present a comparative analysis of the symmetry classified electron spectrum with previously reported results using unrestricted Hartree-Fock calculations (UHF). Both the DFT and UHF calculations produced a non degenerate electronic ground state, not having therefore the necessary condition for a pure JT effect. However, the appearance of a degenerate E$_{g}$ state near to the highest occupied molecular orbital in the DFT calculation, suggests the possibility for a PJT effect responsible for a local distortion of the oxidized CuO$_{6}^{-9}$ cluster.Comment: 12 pages, 3 figures, submitted to International Journal of Modern Physics B (IJMPB

Ground-state degeneracies leave recognizable topological scars in the one-particle density

In Kohn-Sham density functional theory (KS-DFT) a fictitious system of non-interacting particles is constructed having the same ground-state (GS) density as the physical system of interest. A fundamental open question in DFT concerns the ability of an exact KS calculation to spot and characterize the GS degeneracies in the physical system. In this article we provide theoretical evidence suggesting that the GS density, as a function of position on a 2D manifold of parameters affecting the external potential, is "topologically scarred" in a distinct way by degeneracies. These scars are sufficiently detailed to enable determination of the positions of degeneracies and even the associated Berry phases. We conclude that an exact KS calculation can spot and characterize the degeneracies of the physical system

Getting excited: Challenges in quantum-classical studies of excitons in polymeric systems

A combination of classical molecular dynamics (MM/MD) and quantum chemical calculations based on the density functional theory (DFT) was performed to describe conformational properties of diphenylethyne (DPE), methylated-DPE and poly para phenylene ethynylene (PPE). DFT calculations were employed to improve and develop force field parameters for MM/MD simulations. Many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation were utilized to describe excited states of the systems. Reliability of the excitation energies based on the MM/MD conformations was examined and compared to the excitation energies from DFT conformations. The results show an overall agreement between the optical excitations based on MM/MD conformations and DFT conformations. This allows for calculation of excitation energies based on MM/MD conformations

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

An implementation of full self-consistency over the electronic density in the DFT+DMFT framework on the basis of a plane wave-projector augmented wave (PAW) DFT code is presented. It allows for an accurate calculation of the total energy in DFT+DMFT within a plane wave approach. In contrast to frameworks based on the maximally localized Wannier function, the method is easily applied to f electron systems, such as cerium, cerium oxide (Ce2O3) and plutonium oxide (Pu2O3). In order to have a correct and physical calculation of the energy terms, we find that the calculation of the self-consistent density is mandatory. The formalism is general and does not depend on the method used to solve the impurity model. Calculations are carried out within the Hubbard I approximation, which is fast to solve, and gives a good description of strongly correlated insulators. We compare the DFT+DMFT and DFT+U solutions, and underline the qualitative differences of their converged densities. We emphasize that in contrast to DFT+U, DFT+DMFT does not break the spin and orbital symmetry. As a consequence, DFT+DMFT implies, on top of a better physical description of correlated metals and insulators, a reduced occurrence of unphysical metastable solutions in correlated insulators in comparison to DFT+U.Comment: 19 pages, 9 figures. This is an author-created, un-copyedited version of an article accepted for publication in Journal of Physics: Condensed Matter. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at doi: 10.1088/0953-8984/24/7/07560