Double ionization of helium studied with the multi-configuration time-dependent Hartree–Fock method

The intensity dependence of double ionization probability of helium in a strong laser field is investigated by using the multi-configuration time-dependent Hartree–Fock (MCTDHF) method. The results agree with the previous theoretical report by directly solving the time-dependent Schrödinger equation. The time evolution of electronic population on the ground state, electronic energy and dipole moment are also presented and discussed.     

Differentiable programming and density matrix based Hartree–Fock method

Differentiable programming is an emerging programming paradigm that allows people to take derivative of an output of arbitrary code snippet with respect to its input. It is the workhorse behind several well known deep learning frameworks,and has attracted significant attention in scientific machine learning community. In this paper, we introduce and implement a density matrix based Hartree–Fock method that naturally fits into the demands of this paradigm, and demonstrate it by performing fully variational ground state calculation on several representative chemical molecules.     

Linear-scaled excited state calculations at linear response time-dependent Hartree–Fock theory

In this paper, we present a localised molecular orbital (LMO) based methodology of the TDHF excited state calculation in which the computing time is linearly scaled by the size of the system. In the benchmark calculations using simple poly-acetylene molecules, the LMO-driven TDHF provides significant shorter CPU time than conventional TDHF calculations and near O(N) computing cost. We also present the techniques accelerating the convergence speed in Davidson iterative diagonalisation and show its usefulness. The methodology accurately reproduces the excited state properties of poly-acetylene molecules obtained in conventional TDHF calculations.     

Towards a Skyrme–Hartree–Fock–Bogolyubov Mass Formula

In this work, we explain our astrophysical motivations for deriving a mass formula based on HFB calculations with a Skyrme interaction. We give an overview of existing mass formulae and present briefly the last HF+BCS mass formula [1]. The Skyrme force MSk7 [1] is considered in the study of shell effects at N=82, in the neutron-rich region far from stability, within the HFB and HF+BCS theories, and compared with results obtained using the forces SkP^δ and SkP^δρ [2]. This revised version was published online in July 2006 with corrections to the Cover Date.     

Self-consistent theory of finite Fermi systems and Skyrme–Hartree–Fock method

Recent results obtained on the basis of the self-consistent theory of finite Fermi systems by employing the energy density functional proposed by Fayans and his coauthors are surveyed. These results are compared with the predictions of Skyrme–Hartree–Fock theory involving several popular versions of the Skyrme energy density functional. Spherical nuclei are predominantly considered. The charge radii of even and odd nuclei and features of low-lying 2⁺ excitations in semimagic nuclei are discussed briefly. The single-particle energies ofmagic nuclei are examined inmore detail with allowance for corrections to mean-field theory that are induced by particle coupling to low-lying collective surface excitations (phonons). The importance of taking into account, in this problem, nonpole (tadpole) diagrams, which are usually disregarded, is emphasized. The spectroscopic factors of magic and semimagic nuclei are also considered. In this problem, only the surface term stemming from the energy dependence induced in the mass operator by the exchange of surface phonons is usually taken into account. The volume contribution associated with the energy dependence initially present in the mass operator within the self-consistent theory of finite Fermi systems because of the exchange of high-lying particle–hole excitations is also included in the spectroscopic factor. The results of the first studies that employed the Fayans energy density functional for deformed nuclei are also presented.

     

Calculation of open p-shell atoms in the algebraic approach of the Hartree–Fock method

Highly precise calculations of analytical Hartree–Fock orbitals and energies have been performed within the limits of the Roothaan–Hartree–Fock atomic theory (Roothaan–Bagus method) for all open p-shell atoms of the Periodic Table. They were calculated in an algebraic approach using Slater-type atomic orbitals (AOs) as basis functions. Nonlinear parameters (orbital exponents) of AOs were optimized with exceptional accuracy by second-order methods. As a result, it was possible to satisfy exactly the virial relation (10^–14–10^–17) with calculated atomic term energies being close to the Hartree–Fock limit.     

Reconciling phase diffusion and Hartree–Fock approximation in condensate systems

Despite the weakly interacting regime, the physics of Bose–Einstein condensates is widely affected by particle–particle interactions. They determine quantum phase diffusion, which is known to be the main cause of loss of coherence. Studying a simple model of two interacting Bose systems, we show how to predict the appearance of phase diffusion beyond the Bogoliubov approximation, providing a self-consistent treatment in the framework of a generalized Hartree–Fock–Bogoliubov perturbation theory.     

Bogolubov–Hartree–Fock Theory for Strongly Interacting Fermions in the Low Density Limit

We consider the Bogolubov–Hartree–Fock functional for a fermionic many-body system with two-body interactions. For suitable interaction potentials that have a strong enough attractive tail in order to allow for two-body bound states, but are otherwise sufficiently repulsive to guarantee stability of the system, we show that in the low-density limit the ground state of this model consists of a Bose–Einstein condensate of fermion pairs. The latter can be described by means of the Gross–Pitaevskii energy functional.     

Hartree–Fock self-consistent field method for atoms with two open shells of identical symmetry

A generalization of the Roothaan–Bagus method (Roothaan–Hartree–Fock atomic theory) on atoms with open shells of identical symmetry is given. Using orbital exponents of Slater-type atomic orbitals optimized with high accuracy by methods for the minimization of the first and second orders, energy values for atoms with two open s-type shells are calculated within the limits of the Roothaan–Hartree–Fock atomic theory.     

Nonstationary Theory of Perturbations for Open-Shell Atoms in the Hartree–Fock Approximation

For a multielectron open-shell system exposed to an external time-dependent perturbation, the Hartree–Fock nonstationary equations are obtained in terms of density operators. Using them as a basis, equations of nonstationary coupled perturbation theory are suggested in orbital representation within the framework of the two-operator variant of the Roothaan method for an open shell. The perturbation theory corrections to the orbitals have been found in the form of expansions in unperturbed orbitals which are assumed to be calculated in the LCAO approximation in the basis of Slater-type atomic orbitals. The dynamic polarizability of open-shell atoms of substances from Li to F and Sc has been calculated as an even-power series of the frequency of incident radiation.     

Do Dyson Orbitals resemble canonical Hartree–Fock orbitals?

ABSTRACT

Dyson orbitals are overlaps between states with N and N±1 electrons and provide conceptual links between transition probabilities of electron detachment or attachment, density matrices, total energies and general principles of chemical bonding. Canonical, Hartree–Fock orbitals are compared with Dyson orbitals obtained with electron–propagator calculations that retain all elements of the self–energy matrix, wherein all orbital–relaxation and electron–correlation corrections to Koopmans results reside. For valence ionization energies and electron affinities of representative closed–shell molecules, canonical, Hartree–Fock orbitals usually are excellent approximations to Dyson orbitals, although there are some notable cases where the resemblance is not as strong. Numerical relationships between pole strengths and the Koopmans contributions to Dyson orbitals also are inferred from the data.     

A mathematical and computational review of Hartree–Fock SCF methods in quantum chemistry

We present a review of the fundamental topics of Hartree–Fock theory in quantum chemistry. From the molecular Hamiltonian, using and discussing the Born–Oppenheimer approximation, we arrive at the Hartree and Hartree–Fock equations for the electronic problem. Special emphasis is placed on the most relevant mathematical aspects of the theoretical derivation of the final equations, and on the results regarding the existence and uniqueness of their solutions. All Hartree–Fock versions with different spin restrictions are systematically extracted from the general case, thus providing a unifying framework. The discretization of the one-electron orbital space is then reviewed and the Roothaan–Hall formalism introduced. This leads to an exposition of the basic underlying concepts related to the construction and selection of Gaussian basis sets, focusing on algorithmic efficiency issues. Finally, we close the review with a section in which the most relevant modern developments (especially those related to the design of linear-scaling methods) are commented on and linked to the issues discussed. The paper is intentionally introductory and rather self-contained, and may be useful for non-experts intending to use quantum chemical methods in interdisciplinary applications. Moreover, much material that can be found scattered in the literature has been put together to facilitate comprehension and to serve as a handy reference.     

Uniform in N global well-posedness of the time-dependent Hartree–Fock–Bogoliubov equations in $$\mathbb {R}^{1+1}$$

We prove the global well-posedness of the time-dependent Hartree–Fock–Bogoliubov (TDHFB) equations in \(\mathbb {R}^{1+1}\) with two-body interaction potential of the form \(N^{-1}v_N(x) = N^{\beta -1} v(N^\beta x)\) where \(v\ge 0\) is a sufficiently regular radial function, i.e., \(v \in L^1(\mathbb {R})\cap C^\infty (\mathbb {R})\). In particular, using methods of dispersive PDEs similar to the ones used in Grillakis and Machedon (Commun Partial Differ Equ 42:24–67, 2017), we are able to show for any scaling parameter \(\beta >0\) the TDHFB equations are globally well-posed in some Strichartz-type spaces independent of N, cf. (Bach et al. in The time-dependent Hartree–Fock–Bogoliubov equations for Bosons, 2016. arXiv:1602.05171).     

Relativistic Schrödinger Theory and the Hartree–Fock Approach

Within the framework of Relativistic Schrödinger Theory (RST), the scalar two-particle systems with electromagnetic interactions are treated on the basis of a non-Abelian gauge group U(2) which is broken down to the Abelian subgroup U(1)×U(1). In order that the RST dynamics be consistent with the (non-Abelian) Maxwell equations, there arises a compatibility condition which yields cross relationships for the links between the field strengths and currents of both particles such that self-interactions are eliminated. In the non-relativistic limit, the RST dynamics becomes identical to the well-known Hartree–Fock equations (for spinless particles). Consequently the original RST field equations may be considered as the relativistic generalization of the Hartree–Fock equations, and the exchange interactions of the conventional theory (induced by the anti-symmetrization postulate) do reappear here as ordinary gauge interactions due to a broken symmetry.     

Existence of Hartree–Fock excited states for atoms and molecules

For neutral and positively charged atoms and molecules, we prove the existence of infinitely many Hartree–Fock critical points below the first energy threshold (that is, the lowest energy of the same system with one electron removed). This is the equivalent, in Hartree–Fock theory, of the famous Zhislin–Sigalov theorem which states the existence of infinitely many eigenvalues below the bottom of the essential spectrum of the N-particle linear Schrödinger operator. Our result improves a theorem of Lions in 1987 who already constructed infinitely many Hartree–Fock critical points, but with much higher energy. Our main contribution is the proof that the Hartree–Fock functional satisfies the Palais–Smale property below the first energy threshold. We then use minimax methods in the N-particle space, instead of working in the one-particle space.     

Fission barrier of actinide nuclei with double-Λ particles within the Skyrme–Hartree–Fock method

Fission barrier of actinide nuclei including two Λ hyperons is studied in the framework of the Skyrme–Hartree–Fock approach at zero temperature. We adopt the zero-range Skyrme-type interaction between Λ–N and Λ–Λ. Fission barrier is investigated using several parameter sets for ΛΛ interactions. We obtain the result that the barrier height becomes higher as the number of Λ particle increases and the barrier width has a dependence on the ΛΛ interaction. A relation between Λ binding energy and density distribution of Λ particle inside a core nucleus is also discussed. We found that the both Λ particles are attracted into heavier fission fragment.     

Study of Octupole Deformation of Radium Isotopes in the Hartree–Fock–Bogoliubov Approximation with Skyrme Forces

Physics of Atomic Nuclei - The change in the octupole deformation of nuclei in the chain of even–even radium isotopes is studied on the basis of the Hartree–Fock–Bogoliubov method...