Tensor Numerical Methods in Quantum Chemistry: from Hartree-Fock Energy to Excited States

We resume the recent successes of the grid-based tensor numerical methods and discuss their prospects in real-space electronic structure calculations. These methods, based on the low-rank representation of the multidimensional functions and integral operators, led to entirely grid-based tensor-structured 3D Hartree-Fock eigenvalue solver. It benefits from tensor calculation of the core Hamiltonian and two-electron integrals (TEI) in $O(n\log n)$ complexity using the rank-structured approximation of basis functions, electron densities and convolution integral operators all represented on 3D $n\times n\times n$ Cartesian grids. The algorithm for calculating TEI tensor in a form of the Cholesky decomposition is based on multiple factorizations using algebraic 1D ``density fitting`` scheme. The basis functions are not restricted to separable Gaussians, since the analytical integration is substituted by high-precision tensor-structured numerical quadratures. The tensor approaches to post-Hartree-Fock calculations for the MP2 energy correction and for the Bethe-Salpeter excited states, based on using low-rank factorizations and the reduced basis method, were recently introduced. Another direction is related to the recent attempts to develop a tensor-based Hartree-Fock numerical scheme for finite lattice-structured systems, where one of the numerical challenges is the summation of electrostatic potentials of a large number of nuclei. The 3D grid-based tensor method for calculation of a potential sum on a $L\times L\times L$ lattice manifests the linear in $L$ computational work, $O(L)$, instead of the usual $O(L^3 \log L)$ scaling by the Ewald-type approaches

Finite elements and the discrete variable representation in nonequilibrium Green's function calculations. Atomic and molecular models

In this contribution, we discuss the finite-element discrete variable representation (FE-DVR) of the nonequilibrium Green's function and its implications on the description of strongly inhomogeneous quantum systems. In detail, we show that the complementary features of FEs and the DVR allows for a notably more efficient solution of the two-time Schwinger/Keldysh/Kadanoff-Baym equations compared to a general basis approach. Particularly, the use of the FE-DVR leads to an essential speedup in computing the self-energies. As atomic and molecular examples we consider the He atom and the linear version of H$_3^+$ in one spatial dimension. For these closed-shell models we, in Hartree-Fock and second Born approximation, compute the ground-state properties and compare with the exact findings obtained from the solution of the few-particle time-dependent Schr\"odinger equation.Comment: 12 pages, 3 figures, submitted as proceedings of conference "PNGF IV

Efficient grid-based method in nonequilibrium Green's function calculations. Application to model atoms and molecules

We propose and apply the finite-element discrete variable representation to express the nonequilibrium Green's function for strongly inhomogeneous quantum systems. This method is highly favorable against a general basis approach with regard to numerical complexity, memory resources, and computation time. Its flexibility also allows for an accurate representation of spatially extended hamiltonians, and thus opens the way towards a direct solution of the two-time Schwinger/Keldysh/Kadanoff-Baym equations on spatial grids, including e.g. the description of highly excited states in atoms. As first benchmarks, we compute and characterize, in Hartree-Fock and second Born approximation, the ground states of the He atom, the H$_2$ molecule and the LiH molecule in one spatial dimension. Thereby, the ground-state/binding energies, densities and bond-lengths are compared with the direct solution of the time-dependent Schr\"odinger equation.Comment: 11 pages, 5 figures, submitted to Physical Review

Variational Thomas-Fermi Theory of a Nonuniform Bose Condensate at Zero Temperature

We derive a description of the spatially inhomogeneous Bose-Einstein condensate which treats the system locally as a homogeneous system. This approach, similar to the Thomas-Fermi model for the inhomogeneous many-particle fermion system, is well-suited to describe the atomic Bose-Einstein condensates that have recently been obtained experimentally through atomic trapping and cooling. In this paper, we confine our attention to the zero temperature case, although the treatment can be generalized to finite temperatures, as we shall discuss elsewhere.Comment: 24 pages, latex, 6 ps figures, BoxedEPS include

A New Approach To Relativistic Gaussian Basis Functions: Theory And Applications

We present a new hybrid method to solve the relativistic Hartree-Fock-Roothan equations where the one- and two-electron radial integrals are evaluated numerically by defining the basis functions on a grid. This procedure reduces the computational costs in the evaluation of two-electron radial integrals. The orbitals generated by this method are employed to compute the ionization potentials, excitation energies and oscillator strengths of alkali-metal atoms and elements of group IIIA through second order many-body perturbation theor and other correlated theories.Comment: RevTex (15 pages) one figur

Strong-coupling approach for strongly correlated electron systems

A perturbation theory scheme in terms of electron hopping, which is based on the Wick theorem for Hubbard operators, is developed. Diagrammatic series contain single-site vertices connected by hopping lines and it is shown that for each vertex the problem splits into the subspaces with ``vacuum states'' determined by the diagonal Hubbard operators and only excitations around these vacuum states are allowed. The rules to construct diagrams are proposed. In the limit of infinite spatial dimensions the total auxiliary single-site problem exactly splits into subspaces that allows to build an analytical thermodynamically consistent approach for a Hubbard model. Some analytical results are given for the simple approximations when the two-pole (alloy-analogy solution) and four-pole (Hartree-Fock approximation) structure for Green's function is obtained. Two poles describe contribution from the Fermi-liquid component, which is dominant for small electron and hole concentrations (``overdoped case'' of high-$T_c$'s), whereas other two describe contribution from the non-Fermi liquid and are dominant close to half-filling (``underdoped case'').Comment: 14 pages, revtex, feynmf, 5 EPS figures, two-column PRB style, published in PR

Collective excitations in trapped boson-fermion mixtures: from demixing to collapse

We calculate the spectrum of low-lying collective excitations in a gaseous cloud formed by a Bose-Einstein condensate and a spin-polarized Fermi gas over a range of the boson-fermion coupling strength extending from strongly repulsive to strongly attractive. Increasing boson-fermion repulsions drive the system towards spatial separation of its components (``demixing''), whereas boson-fermion attractions drive it towards implosion (``collapse''). The dynamics of the system is treated in the experimentally relevant collisionless regime by means of a Random-Phase approximation and the behavior of a mesoscopic cloud under isotropic harmonic confinement is contrasted with that of a macroscopic mixture at given average particle densities. In the latter case the locations of both the demixing and the collapse phase transitions are sharply defined by the same stability condition, which is determined by the softening of an eigenmode of either fermionic or bosonic origin. In contrast, the transitions to either demixing or collapse in a mesoscopic cloud at fixed confinement and particle numbers are spread out over a range of boson-fermion coupling strength, and some initial decrease of the frequencies of a set of collective modes is followed by hardening as evidenced by blue shifts of most eigenmodes. The spectral hardening can serve as a signal of the impending transition and is most evident when the number of bosons in the cloud is relatively large. We propose physical interpretations for these dynamical behaviors with the help of suitably defined partial compressibilities for the gaseous cloud under confinement.Comment: 16 pages, 7 figures, revtex