Open-boundary Ehrenfest molecular dynamics: towards a model of current unduced heating in nanowires

We present a time-dependent method based on the single-particle electron density matrix that allows the electronic and ionic degrees of freedom to be modelled within the Ehrenfest approximation in the presence of open boundaries. We describe a practical implementation using tight binding, and use it to investigate steady-state conduction through a single-atom device and to perform molecular dynamics. We find that in the Ehrenfest approximation an electric current allows both ionic heating and cooling to take place, depending on the bias

Block bond-order potential as a convergent moments-based method

The theory of a novel bond-order potential, which is based on the block Lanczos algorithm, is presented within an orthogonal tight-binding representation. The block scheme handles automatically the very different character of sigma and pi bonds by introducing block elements, which produces rapid convergence of the energies and forces within insulators, semiconductors, metals, and molecules. The method gives the first convergent results for vacancies in semiconductors using a moments-based method with a low number of moments. Our use of the Lanczos basis simplifies the calculations of the band energy and forces, which allows the application of the method to the molecular dynamics simulations of large systems. As an illustration of this convergent O(N) method we apply the block bond-order potential to the large scale simulation of the deformation of a carbon nanotube.Comment: revtex, 43 pages, 11 figures, submitted to Phys. Rev.

Efficient Recursion Method for Inverting Overlap Matrix

A new O(N) algorithm based on a recursion method, in which the computational effort is proportional to the number of atoms N, is presented for calculating the inverse of an overlap matrix which is needed in electronic structure calculations with the the non-orthogonal localized basis set. This efficient inverting method can be incorporated in several O(N) methods for diagonalization of a generalized secular equation. By studying convergence properties of the 1-norm of an error matrix for diamond and fcc Al, this method is compared to three other O(N) methods (the divide method, Taylor expansion method, and Hotelling's method) with regard to computational accuracy and efficiency within the density functional theory. The test calculations show that the new method is about one-hundred times faster than the divide method in computational time to achieve the same convergence for both diamond and fcc Al, while the Taylor expansion method and Hotelling's method suffer from numerical instabilities in most cases.Comment: 17 pages and 4 figure

Systematic generation of finite-range atomic basis sets for linear-scaling calculations

Basis sets of atomic orbitals are very efficient for density functional calculations but lack a systematic variational convergence. We present a variational method to optimize numerical atomic orbitals using a single parameter to control their range. The efficiency of the basis generation scheme is tested and compared with other schemes for multiple zeta basis sets. The scheme shows to be comparable in quality to other widely used schemes albeit offering better performance for linear-scaling computations

First-principles quantum transport modeling of thermoelectricity in single-molecule nanojunctions with graphene nanoribbon electrodes

We overview nonequilibrium Green function combined with density functional theory (NEGF-DFT) modeling of independent electron and phonon transport in nanojunctions with applications focused on a new class of thermoelectric devices where a single molecule is attached to two metallic zigzag graphene nanoribbons (ZGNRs) via highly transparent contacts. Such contacts make possible injection of evanescent wavefunctions from ZGNRs, so that their overlap within the molecular region generates a peak in the electronic transmission. Additionally, the spatial symmetry properties of the transverse propagating states in the ZGNR electrodes suppress hole-like contributions to the thermopower. Thus optimized thermopower, together with diminished phonon conductance through a ZGNR/molecule/ZGNR inhomogeneous structure, yields the thermoelectric figure of merit ZT~0.5 at room temperature and 0.5<ZT<2.5 below liquid nitrogen temperature. The reliance on evanescent mode transport and symmetry of propagating states in the electrodes makes the electronic-transport-determined power factor in this class of devices largely insensitive to the type of sufficiently short conjugated organic molecule, which we demonstrate by showing that both 18-annulene and C10 molecule sandwiched by the two ZGNR electrodes yield similar thermopower. Thus, one can search for molecules that will further reduce the phonon thermal conductance (in the denominator of ZT) while keeping the electronic power factor (in the nominator of ZT) optimized. We also show how often employed Brenner empirical interatomic potential for hydrocarbon systems fails to describe phonon transport in our single-molecule nanojunctions when contrasted with first-principles results obtained via NEGF-DFT methodology.Comment: 20 pages, 6 figures; mini-review article prepared for the special issue of the Journal of Computational Electronics on "Simulation of Thermal, Thermoelectric, and Electrothermal Phenomena in Nanostructures", edited by I. Knezevic and Z. Aksamij