Electronic structure calculations and molecular dynamics simulations with linear system-size scaling

We review our recently developed electronic structure calculation methods used for the dynamics of large-scale solids or liquids with an efficient algorithm for large scale simultaneous linear equations. The electronic structure calculation method is the `atomic superposition and electron delocalization molecular orbitals theory' (ASED), using the Mulliken charge density. Very crucial algorithm is the generalized shifted COCG (conjugate orthogonal conjugate gradient) method b...

This article is a pedagogical introduction to density-functional tight-binding (DFTB) method. We derive it from the density-functional theory, give the details behind the tight-binding formalism, and give practical recipes for parametrization: how to calculate pseudo-atomic orbitals and matrix elements, and especially how to systematically fit the short-range repulsions. Our scope is neither to provide a historical review nor to make performance comparisons, but to give begin...

Electronic structure calculation of atoms and molecules, in the past few decades has largely been dominated by density functional methods. This is primarily due to the fact that this can account for electron correlation effects in a rigorous, tractable manner keeping the computational cost at a manageable level. With recent advances in methodological development, algorithmic progress as well as computer technology, larger physical, chemical and biological systems are amenable...

Linear-scaling electronic structure methods based on the calculation of moments of the underlying electronic Hamiltonian offer a computationally efficient and numerically robust scheme to drive large-scale atomistic simulations, in which the quantum-mechanical nature of the electrons is explicitly taken into account. We compare the kernel polynomial method to the Fermi operator expansion method and establish a formal connection between the two approaches. We show that the con...

We present in detail the recently derived ab-initio molecular dynamics (AIMD) formalism [Phys. Rev. Lett. 101 096403 (2008)], which due to its numerical properties, is ideal for simulating the dynamics of systems containing thousands of atoms. A major drawback of traditional AIMD methods is the necessity to enforce the orthogonalization of the wave-functions, which can become the bottleneck for very large systems. Alternatively, one can handle the electron-ion dynamics within...

We develop a local correlation variant of auxiliary field quantum Monte Carlo (AFQMC) that is based on local natural orbitals (LNO-AFQMC). In LNO-AFQMC, independent AFQMC calculations are performed for each localized occupied orbital using a truncated set of tailored orbitals. Because the size of this space does not grow with system size for a target accuracy, the method has linear scaling. Applying LNO AFQMC to molecular problems containing a few hundred to a thousand orbita...

Routine applications of electronic structure theory to molecules and periodic systems need to compute the electron density from given Hamiltonian and, in case of non-orthogonal basis sets, overlap matrices. System sizes can range from few to thousands or, in some examples, millions of atoms. Different discretization schemes (basis sets) and different system geometries (finite non-periodic vs. infinite periodic boundary conditions) yield matrices with different structures. The...

In this paper, we propose an orbital iteration based parallel approach for electronic structure calculations. This approach is based on our understanding of the single-particle equations of independent particles that move in an effective potential. With this new approach, the solution of the single-particle equation is reduced to some solutions of independent linear algebraic systems and a small scale algebraic problem. It is demonstrated by our numerical experiments that thi...

Graph-based linear scaling electronic structure theory for quantum-mechanical molecular dynamics simulations is adapted to the most recent shadow potential formulations of extended Lagrangian Born-Oppenheimer molecular dynamics, including fractional molecular-orbital occupation numbers, which enables stable simulations of sensitive complex chemical systems with unsteady charge solutions. The proposed formulation includes a preconditioned Krylov subspace approximation for the ...

We propose a general method for constructing system-dependent basis functions for correlated quantum chemical calculations. Our construction combines features from several traditional approaches: plane waves, localized basis functions, and wavelets. In a one-dimensional mimic of Coulomb systems, it requires only 2-3 basis functions per electron to achieve chemical accuracy, and reproduces the natural orbitals. We illustrate its effectiveness for molecular energy curves and ch...