Standard Hartree-Fock Research Articles

Transcorrelated selected configuration interaction in a bi-orthonormal basis and with a cheap three-body correlation factor.

In this work, we develop a mathematical framework for a selected configuration interaction (SCI) algorithm within a bi-orthogonal basis for transcorrelated (TC) calculations. The bi-orthogonal basis used here serves as the equivalent of the standard Hartree-Fock (HF) orbitals. However, within the context of TC, it leads to distinct orbitals for the left and right vectors. Our findings indicate that the use of such a bi-orthogonal basis allows for a proper definition of the frozen core approximation. In contrast, the use of HF orbitals results in bad error cancellations for ionization potentials and atomization energies (AE). Compared to HF orbitals, the optimized bi-orthogonal basis significantly reduces the positive part of the second-order energy (PT2), thereby facilitating the use of standard extrapolation techniques of hermitian SCI. While we did not observe a significant improvement in the convergence of the SCI algorithm, this is largely due to the use in this work of a simple three-body correlation factor introduced in a recent study. This correlation factor, which depends only on atomic parameters, eliminates the need for re-optimization of the correlation factor for molecular systems, making its use straightforward and user-friendly. Despite the simplicity of this correlation factor, we were able to achieve accurate results on the AE of a series of 14 molecules on a triple-zeta basis. We also successfully broke a double bond until the full dissociation limit while maintaining the size consistency property. This work thus demonstrates the potential of the BiO-TC-SCI approach in handling complex molecular systems.

Approximation of the ground and excited states of atoms and molecules with a single determinant by means of the exact many-particle Hamiltonian

In the present work, we search for the maximum of the functional | ⟨ Φ ′ | H ^ | Φ ⟩ | , where | Φ ′ ⟩ is a Slater Determinant (SlDet) and H ^ is the exact Hamiltonian of an atom or a molecule, starting from a SlDet | Φ ⟩ , with its spin orbitals calculated by the standard Hartree-Fock (HF) equation or other approximation or any determinant. The element | ⟨ Φ 1 | H ^ | Φ ⟩ | with | Φ 1 ⟩ the maximising | Φ ′ ⟩ gives a value greater or equal to | ⟨ Φ | H ^ | Φ ⟩ | . Next we calculate the corresponding maximum overlap | ⟨ Φ 2 | H ^ | Φ 1 ⟩ | and finally | ⟨ Φ n + 1 | H ^ | Φ n ⟩ | until | ⟨ Φ n + 1 | H ^ | Φ n ⟩ − ⟨ Φ n | H ^ | Φ n − 1 ⟩ | ≤ ε , where ε determines the desired numerical accuracy. We show that the sequence ⟨ Φ n + 1 | H ^ | Φ n ⟩ converges to an extremum ⟨ Φ | H ^ | Φ ⟩ . Having found the SlDet with the lowest energy we repeat the procedure in the orthogonal subspace for finding the first and the higher excited states. We applied this method in order to determine the energies of several configurations of H 3 , the Lithium atom, LiH and Be.

Particle-Breaking Hartree-Fock Theory for Open Molecular Systems.

In this work we present the particle-breaking Hartree-Fock (PBHF) model which is a mean-field approach to open molecular systems. The interaction of a system with the environment is parametrized through a particle-breaking term in the molecular Hamiltonian. The PBHF wave function is constructed through an exponential unitary transformation of a Slater determinant with a given number of electrons. We consider only the closed-shell formalism. The parametrization results in a linear combination of Slater determinants with different numbers of electrons, i.e., the PBHF wave function is not an eigenfunction of the number operator. As a result, the density matrix may have fractional occupations which are, because of the unitary parametrization, always between 0.0 and 2.0. The occupations are optimized simultaneously with the orbitals, using the trust-region optimization procedure. In the limit of a particle-conserving Hamiltonian, the PBHF optimization will converge to a standard Hartree-Fock wave function. We show that the average number of electrons may be decreased or increased depending on whether the particle-breaking term affects occupied or virtual orbitals.

Photoionization and core resonances from range-separated density-functional theory: General formalism and example of the beryllium atom.

We explore the merits of linear-response range-separated time-dependent density-functional theory (TDDFT) for the calculation of photoionization spectra. We consider two variants of range-separated TDDFT, namely, the time-dependent range-separated hybrid (TDRSH) scheme, which uses a global range-separation parameter, and the time-dependent locally range-separated hybrid (TDLRSH), which uses a local range-separation parameter, and compare with standard time-dependent local-density approximation (TDLDA) and time-dependent Hartree-Fock (TDHF). We show how to calculate photoionization spectra with these methods using the Sternheimer approach formulated in a non-orthogonal B-spline basis set with appropriate frequency-dependent boundary conditions. We illustrate these methods on the photoionization spectrum of the Be atom, focusing, in particular, on the core resonances. Both the TDRSH and TDLRSH photoionization spectra are found to constitute a large improvement over the TDLDA photoionization spectrum and a more modest improvement over the TDHF photoionization spectrum.

Third-Order Møller-Plesset Theory Made More Useful? The Role of Density Functional Theory Orbitals.

The practical utility of Møller-Plesset (MP) perturbation theory is severely constrained by the use of Hartree-Fock (HF) orbitals. It has recently been shown that the use of regularized orbital-optimized MP2 orbitals and scaling of MP3 energy could lead to a significant reduction in MP3 error [Bertels, L. W.; J. Phys. Chem. Lett. 2019, 10, 4170 4176]. In this work, we examine whether density functional theory (DFT)-optimized orbitals can be similarly employed to improve the performance of MP theory at both the MP2 and MP3 levels. We find that the use of DFT orbitals leads to significantly improved performance for prediction of thermochemistry, barrier heights, noncovalent interactions, and dipole moments relative to the standard HF-based MP theory. Indeed, MP3 (with or without scaling) with DFT orbitals is found to surpass the accuracy of coupled-cluster singles and doubles (CCSD) for several data sets. We also found that the results are not particularly functional sensitive in most cases (although range-separated hybrid functionals with low delocalization error perform the best). MP3 based on DFT orbitals thus appears to be an efficient, noniterative O(N6) scaling wave-function approach for single-reference electronic structure computations. Scaled MP2 with DFT orbitals is also found to be quite accurate in many cases, although modern double hybrid functionals are likely to be considerably more accurate.

Linear-response range-separated density-functional theory for atomic photoexcitation and photoionization spectra.

We investigate the performance of the range-separated hybrid (RSH) scheme, which combines long-range Hartree-Fock (HF) and a short-range density-functional approximation (DFA), for calculating the photoexcitation/photoionization spectra of the H and He atoms, using a B-spline basis set in order to correctly describe the continuum part of the spectra. The study of these simple systems allows us to quantify the influence on the spectra of the errors coming from the short-range exchange-correlation DFA and from the missing long-range correlation in the RSH scheme. We study the differences using the long-range HF exchange (nonlocal) potential and the long-range exact exchange (local) potential. Contrary to the former, the latter supports a series of Rydberg states and gives reasonable photoexcitation/photoionization spectra, even without applying linear-response theory. The most accurate spectra are obtained with the linear-response time-dependent RSH (TDRSH) scheme. In particular, for the He atom at the optimal value of the range-separation parameter, TDRSH gives slightly more accurate photoexcitation and photoionization spectra than the standard linear-response time-dependent HF. More generally, this work shows the potential of range-separated density-functional theory for calculating linear and nonlinear optical properties involving continuum states.

Nuclear electromagnetic dipole response with the self-consistent Green's function formalism

Microscopic calculations of the electromagnetic response of medium-mass nuclei are now feasible thanks to the availability of realistic nuclear interactions with accurate saturation and spectroscopic properties, and the development of large-scale computing methods for many-body physics. The purpose is to compute isovector dipole electromagnetic (E1) response and related quantities, i.e. integrated dipole cross section and polarizability, and compare with data from photoabsorption and Coulomb excitation experiments. The single-particle propagator is obtained by solving the Dyson equation, where the self-energy includes correlations non-perturbatively through the Algebraic Diagrammatic Construction (ADC) method. The particle-hole ($ph$) polarization propagator is treated in the Dressed Random Phase Approximation (DRPA), based on an effective correlated propagator that includes some $2p2h$ effects but keeps the same computation scaling as the standard Hartree-Fock propagator. The E1 responses for $^{14,16,22,24}$O, $^{36,40,48,52,54,70}$Ca and $^{68}$Ni have been computed: the presence of a soft dipole mode of excitation for neutron-rich nuclei is found, and there is a fair reproduction of the low-energy part of the experimental excitation spectrum. This is reflected in a good agreement with the empirical dipole polarizability values. For a realistic interaction with an accurate reproduction of masses and radii up to medium-mass nuclei, the Self-Consistent Green's Function method provides a good description of the E1 response, especially in the part of the excitation spectrum below the Giant Dipole Resonance. The dipole polarizability is largely independent from the strategy of mapping the dressed propagator to a simplified one that is computationally manageable

An Efficient Hartree-Fock Implementation Based on the Contraction of Integrals in the Primitive Basis.

A new approach to implement the restricted closed-shell Hartree-Fock equation is proposed. In the ansatz presented, the explicit transformation of integrals from the primitive to the atomic-orbital basis is omitted. Instead, the density matrix is transformed to the primitive basis, in which it is contracted with the untransformed integrals. Obtained is the two-electron part of the Fock matrix, which is transformed back to the atomic orbital basis. The remaining steps of the self-consistent field algorithm are then performed as usual. The program presented here incorporates the most important standard techniques, such as integral prescreening, convergence acceleration (via the direct inversion of the iterative subspace ansatz), and the differential density scheme. Test calculations on standard Hartree-Fock problems were compared to the commercially available MOLPRO and TURBOMOLE program packages. Except in a few special cases, the performance of the program presented here is superior, in comparison to those two programs. Accelerations by up to a factor of 5 were found, with respect to MOLPRO calculations, and up to 3 for TURBOMOLE (in the latter case, up to 55 for generalized contracted basis sets). The program structure is independent of the type of radial contraction; however, the best results are obtained for generalized radial contraction basis sets of low contraction. The program is written in C++ and utilizes code generation engines to automatically generate the routines for the integration and density contraction. Streaming SIMD extensions are used explicitly.

Screening mixing GW/Bethe–Salpeter approach for triplet states of organic molecules

We recently proposed a screening mixing many-body ansatz (Ziaei and Bredow 2017 Phys. Rev. B 96 195115) to decrease the typical overestimation of the Hartree–Fock based GW/Bethe–Salpeter equation (BSE) singlet–singlet excitation energies in molecular systems. Now we have evaluated the accuracy of the proposed scheme for triplet states of a set of 20 organic molecules known as the Thiel set. We show that by mixing different screenings into GW and BSE calculated within random phase approximation (in order to ensure best gap and an optimal exciton binding energy), the total mean absolute error of 0.59 eV in the standard Hartree–Fock based eigenvalue GW/BSE approach is reduced to 0.26 eV for 63 triplet states. We further demonstrate that the quasi-particle self-consistent GW/BSE approach in which orbitals and energies are updated in the Green’s function and the dynamically screened interaction mostly and considerably underestimates the excitation energies as shown for a few molecules.

Spin-orbit interaction in relativistic nuclear structure models

Relativistic self-consistent mean-field (SCMF) models naturally account for the coupling of the nucleon spin to its orbital motion, whereas non-relativistic SCMF methods necessitate a phenomenological ansatz for the effective spin-orbit potential. Recent experimental studies aim to explore the isospin properties of the effective spin-orbit interaction in nuclei. SCMF models are very useful in the interpretation of the corresponding data, however standard relativistic mean-field and non-relativistic Hartree-Fock models use effective spin-orbit potentials with different isovector properties, mainly because exchange contributions are not treated explicitly in the former. The impact of exchange terms on the effective spin-orbit potential in relativistic mean-field models is analysed, and it is shown that it leads to an isovector structure similar to the one used in standard non-relativistic Hartree-Fock. Data on the isospin dependence of spin-orbit splittings in spherical nuclei could be used to constrain the isovector-scalar channel of relativistic mean-field models. The reproduction of the empirical kink in the isotope shifts of even Pb nuclei by relativistic effective interactions points to the occurrence of pseudospin symmetry in the single-neutron spectra in these nuclei.

Fractional-charge and fractional-spin errors in range-separated density-functional theory

ABSTRACTWe investigate fractional-charge and fractional-spin errors in range-separated density-functional theory (DFT). Specifically, we consider the range-separated hybrid (RSH) method which combines long-range Hartree-Fock (HF) exchange with a short-range semilocal exchange-correlation density functional, and the RSH+MP2 method which adds long-range, second-order Møller-Plesset (MP2) correlation. Results on atoms and molecules show that the fractional-charge errors obtained in RSH are much smaller than in the standard Kohn-Sham (KS) scheme applied with semilocal or hybrid approximations, and also generally smaller than in the standard HF method. The RSH+MP2 method tends to have smaller fractional-charge errors than standard MP2 for the most diffuse systems, but larger fractional-charge errors for the more compact systems. Even though the individual contributions to the fractional-spin errors in the H atom coming from the short-range exchange and correlation density-functional approximations are smaller than the corresponding contributions for the full-range exchange and correlation density-functional approximations, RSH gives fractional-spin errors that are larger than in the standard KS scheme and only slightly smaller than in standard HF. Adding long-range MP2 correlation only leads to infinite fractional-spin errors. This work clarifies the successes and limitations of range-separated DFT approaches for eliminating self-interaction and static-correlation errors.

Modeling molecule-plasmon interactions using quantized radiation fields within time-dependent electronic structure theory.

We present a combined cavity quantum electrodynamics/ab initio electronic structure approach for simulating plasmon-molecule interactions in the time domain. The simple Jaynes-Cummings-type model Hamiltonian typically utilized in such simulations is replaced with one in which the molecular component of the coupled system is treated in a fully ab initio way, resulting in a computationally efficient description of general plasmon-molecule interactions. Mutual polarization effects are easily incorporated within a standard ground-state Hartree-Fock computation, and time-dependent simulations carry the same formal computational scaling as real-time time-dependent Hartree-Fock theory. As a proof of principle, we apply this generalized method to the emergence of a Fano-like resonance in coupled molecule-plasmon systems; this feature is quite sensitive to the nanoparticle-molecule separation and the orientation of the molecule relative to the polarization of the external electric field.

Extended Hartree-Fock study of the single-particle potential: The nuclear symmetry energy, nucleon effective mass, and folding model of the nucleon optical potential

The nucleon mean-field potential has been thoroughly investigated in an extended Hartree-Fock (HF) calculation of nuclear matter (NM) using the CDM3Y3 and CDM3Y6 density dependent versions of the M3Y interaction. The single-particle (SP) energies of nucleons in NM are determined according to the Hugenholtz--Van Hove theorem, which gives rise naturally to a rearrangement term (RT) of the SP potential at the Fermi momentum. Using the RT obtained exactly at the different NM densities and neutron-proton asymmetries, a consistent method is suggested to take into account effectively the momentum dependence of the RT of the SP potential within the standard HF scheme. To obtain a realistic momentum dependence of the nucleon optical potential (OP), the high-momentum part of the SP potential was accurately readjusted to reproduce the observed energy dependence of the nucleon OP over a wide range of energies. The impact of the RT and momentum dependence of the SP potential on the density dependence of the nuclear symmetry energy and nucleon effective mass has been studied in detail. The high-momentum tail of the SP potential was found to have a sizable effect on the slope of the symmetry energy and the neutron-proton effective mass splitting at supranuclear densities of the NM. Based on a local density approximation, the folding model of the nucleon OP of finite nuclei has been extended to take into account consistently the RT and momentum dependence of the nucleon OP in the same mean-field manner, and successfully applied to study the elastic neutron scattering on the lead target at the energies around the Fermi energy.

Configuration interaction singles based on the real-space numerical grid method: Kohn-Sham versus Hartree-Fock orbitals.

We developed a program code of configuration interaction singles (CIS) based on a numerical grid method. We used Kohn-Sham (KS) as well as Hartree-Fock (HF) orbitals as a reference configuration and Lagrange-sinc functions as a basis set. Our calculations show that KS-CIS is more cost-effective and more accurate than HF-CIS. The former is due to the fact that the non-local HF exchange potential greatly reduces the sparsity of the Hamiltonian matrix in grid-based methods. The latter is because the energy gaps between KS occupied and virtual orbitals are already closer to vertical excitation energies and thus KS-CIS needs small corrections, whereas HF results in much larger energy gaps and more diffuse virtual orbitals. KS-CIS using the Lagrange-sinc basis set also shows a better or a similar accuracy to smaller orbital space compared to the standard HF-CIS using Gaussian basis sets. In particular, KS orbitals from an exact exchange potential by the Krieger-Li-Iafrate approximation lead to more accurate excitation energies than those from conventional (semi-) local exchange-correlation potentials.

An equation of motion analysis of the two stage Kondo effect in T-shaped double-quantum-dot systems

We use the equation of motion method in connection with a generalized Anderson Hamiltonian to evaluate the electronic transmission in a T-shaped double quantum dot system. We consider the strong Coulomb interaction regime (U1→∞, U2→∞) using a decoupling procedure that includes terms beyond the standard Hartree–Fock approximation. The typical manifestation of the two stage Kondo effect is reflected in system's electronic transmission coefficient that presents both a large Lorentzian and a sharp dip around ω=0. We provide an analytical result for the first stage Kondo temperature that includes corrections due to the presence of an additional quantum dot in the system. For the second stage Kondo effect, we identify the logarithmic correction that is responsible for the additional dip in the system's electronic transmission coefficient.

Hartree-Fock-Bogoliubov calculations of deformed weakly bound nuclei using continuous bases

The Hartree-Fock-Bogoliubov equations for deformed weakly bound nuclei are solved using a basis of Poschl-Teller-Ginocchio and Bessel/Coulomb wave functions, which possess proper asymptotic behavior. Results compare well with standard Hartree-Fock- Bogoliubov calculations using box boundary condition or transformed harmonic oscillator basis.

Excitation picture of an interacting Bose gas

Atomic Bose–Einstein condensates (BECs) can be viewed as macroscopic objects where atoms form correlated atom clusters to all orders. Therefore, the presence of a BEC makes the direct use of the cluster-expansion approach–lucrative e.g. in semiconductor quantum optics–inefficient when solving the many-body kinetics of a strongly interacting Bose. An excitation picture is introduced with a nonunitary transformation that describes the system in terms of atom clusters within the normal component alone. The nontrivial properties of this transformation are systematically studied, which yields a cluster-expansion friendly formalism for a strongly interacting Bose gas. Its connections and corrections to the standard Hartree–Fock–Bogoliubov approach are discussed and the role of the order parameter and the Bogoliubov excitations are identified. The resulting interaction effects are shown to visibly modify number fluctuations of the BEC. Even when the BEC has a nearly perfect second-order coherence, the BEC number fluctuations can still resolve interaction-generated non-Poissonian fluctuations.

Global solutions of Hartree-Fock theory and their consequences for strongly correlated quantum systems

We present a density matrix approach for computing global solutions of Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems. Equality of the upper- and lower-bound energies guarantees that the computed solution is the globally optimal solution of Hartree-Fock theory. For strongly correlated systems the SDP approach requires us to reassess the accuracy of the Hartree-Fock energies and densities from standard software packages for electronic structure theory. Calculations of the H$_{4}$ dimer and N$_{2}$ molecule show that the energies from SDP Hartree-Fock are lower than those from standard Hartree-Fock methods by 100-200 kcal/mol in the dissociation region. The present findings have important consequences for the computation and interpretation of electron correlation, which is typically defined relative to the Hartree-Fock energy and density.

The extended Koopmans' theorem for orbital-optimized methods: Accurate computation of ionization potentials

The extended Koopmans' theorem (EKT) provides a straightforward way to compute ionization potentials (IPs) from any level of theory, in principle. However, for non-variational methods, such as Møller-Plesset perturbation and coupled-cluster theories, the EKT computations can only be performed as by-products of analytic gradients as the relaxed generalized Fock matrix (GFM) and one- and two-particle density matrices (OPDM and TPDM, respectively) are required [J. Cioslowski, P. Piskorz, and G. Liu, J. Chem. Phys. 107, 6804 (1997)]. However, for the orbital-optimized methods both the GFM and OPDM are readily available and symmetric, as opposed to the standard post Hartree-Fock (HF) methods. Further, the orbital optimized methods solve the N-representability problem, which may arise when the relaxed particle density matrices are employed for the standard methods, by disregarding the orbital Z-vector contributions for the OPDM. Moreover, for challenging chemical systems, where spin or spatial symmetry-breaking problems are observed, the abnormal orbital response contributions arising from the numerical instabilities in the HF molecular orbital Hessian can be avoided by the orbital-optimization. Hence, it appears that the orbital-optimized methods are the most natural choice for the study of the EKT. In this research, the EKT for the orbital-optimized methods, such as orbital-optimized second- and third-order Møller-Plesset perturbation [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)] and coupled-electron pair theories [OCEPA(0)] [U. Bozkaya and C. D. Sherrill, J. Chem. Phys. 139, 054104 (2013)], are presented. The presented methods are applied to IPs of the second- and third-row atoms, and closed- and open-shell molecules. Performances of the orbital-optimized methods are compared with those of the counterpart standard methods. Especially, results of the OCEPA(0) method (with the aug-cc-pVTZ basis set) for the lowest IPs of the considered atoms and closed-shell molecules are substantially accurate, the corresponding mean absolute errors are 0.11 and 0.15 eV, respectively.

THE 1D HEISENBERG ANTIFERROMAGNET MODEL BY THE VARIATION AFTER PROJECTION METHOD

The four site and eight site 1D anti-ferromagnetic Heisenberg chains in the Jordan–Wigner representation are investigated within the standard Hartree–Fock and random phase approximation (RPA) approaches, both in the symmetry unbroken and in the symmetry broken phases. A translation invariant groundstate, obtained by the projection method as a linear combination of a symmetry-broken HF state and its image under reflection, is also considered, for each chain type. It is found that the projection method considerably improves the HF treatment for instance as far as the groundstate energy is concerned, but also with respect to the RPA energies. The results are furthermore confronted with the ones obtained within so-called SCRPA scheme.