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This work is concerned with two-spin-1/2-fermion relativistic quantum mechanics, and it is about the construction of one-particle projectors using an inherently two(many)-particle, `explicitly correlated' basis representation, necessary for good numerical convergence of the interaction energy. It is demonstrated that a faithful representation of the one-particle operators, which appear in intermediate but essential computational steps, can be constructed over a many-particle basis set by accounting for the full Hilbert space beyond the physically relevant anti-symmetric subspace. Applications of this development can be foreseen for the computation of quantum-electrodynamics corrections for a correlated relativistic reference state and high-precision relativistic computations of medium-to-high-$Z$ helium-like systems, for which other two-particle projection techniques are unreliable.

The development of computational resources has made it possible to determine upper bounds for atomic and molecular energies with high precision. Yet, error bounds to the computed energies have been available only as estimates. In this paper, the Pollak-Martinazzo lower-bound theory, in conjunction with correlated Gaussian basis sets, is elaborated and implemented to provide sub-parts-per-million convergence of the ground- and excited-state energies for the He, Li, and Be atoms. The quality of the lower bounds is comparable to that of the upper bounds obtained from the Ritz method. These results exemplify the power of lower bounds to provide tight estimates of atomic energies.

The triplet contribution is computed to the 1 and 2 $^1S^\text{e}_0$ states of the He atom, to the $1\ ^1S^\text{e}_0$ state of the Li$^+$ and Be${^{2+}}$ ions, and to the $X\ ^1\Sigma_\text{g}^+$ ground state of the H$_2$ molecule by extensive use of double-group symmetry (equivalent to $LS$ coupling for the atomic systems) during the course of the variational solution of the no-pair Dirac-Coulomb-Breit wave equation. The no-pair Dirac-Coulomb-Breit energies are converged within a sub-parts-per-billion relative precision using an explicitly correlated Gaussian basis optimized to the non-relativistic energies. The $\alpha$ fine-structure constant dependence of the triplet sector contribution to the variational energy is $\alpha^4E_\text{h}$ at leading order, in agreement with the formal perturbation theory result available from the literature.

Interactions in atomic and molecular systems are dominated by electromagnetic forces and the theoretical framework must be in the quantum regime. The physical theory for the combination of quantum mechanics and electromagnetism, quantum electrodynamics has been established by the mid-twentieth century, primarily as a scattering theory. To describe atoms and molecules, it is important to consider bound states. In the non-relativistic quantum mechanics framework, bound states can be efficiently computed using robust and general methodologies with systematic approximations developed for solving wave equations. With the sight of the development of a computational quantum electrodynamics framework for atomic and molecular matter, the field theoretic Bethe-Salpeter wave equation expressed in space-time coordinates, its exact equal-time variant and emergence of a relativistic wave equation is reviewed. A computational framework, with initial applications and future challenges in relation with precision spectroscopy, is also highlighted.

Variational and perturbative relativistic energies are computed and compared for two-electron atoms and molecules with low nuclear charge numbers. In general, good agreement of the two approaches is observed. Remaining deviations can be attributed to higher-order relativistic, also called non-radiative quantum electrodynamics (QED), corrections of the perturbative approach that are automatically included in the variational solution of the no-pair Dirac$-$Coulomb$-$Breit (DCB) equation to all orders of the $\alpha$ fine-structure constant. The analysis of the polynomial $\alpha$ dependence of the DCB energy makes it possible to determine the leading-order relativistic correction to the non-relativistic energy to high precision without regularization. Contributions from the Breit$-$Pauli Hamiltonian, for which expectation values converge slowly due the singular terms, are implicitly included in the variational procedure. The $\alpha$ dependence of the no-pair DCB energy shows that the higher-order ($\alpha^4 E_\mathrm{h}$) non-radiative QED correction is 5 % of the leading-order ($\alpha^3 E_\mathrm{h}$) non-radiative QED correction for $Z=2$ (He), but it is 40 % already for $Z=4$ (Be$^{2+}$), which indicates that resummation provided by the variational procedure is important already for intermediate nuclear charge numbers.

The Breit interaction is implemented in the no-pair variational Dirac-Coulomb (DC) framework using an explicitly correlated Gaussian basis reported in the previous paper [Paper I: P. Jeszenszki, D. Ferenc, and E. M\'atyus (2022)]. Both a perturbative and a fully variational inclusion of the Breit term is considered. The no-pair DC plus perturbative Breit as well as the no-pair Dirac-Coulomb-Breit energies are compared with perturbation theory results including the Breit-Pauli Hamiltonian and leading-order non-radiative quantum electrodynamics corrections for low $Z$ values. Possible reasons for the observed deviations are discussed.

The Dirac-Coulomb equation with positive-energy projection is solved using explicitly correlated Gaussian functions. The algorithm and computational procedure aims for a parts-per-billion convergence of the energy to provide a starting point for further comparison and further developments in relation with high-resolution atomic and molecular spectroscopy. Besides a detailed discussion of the implementation of the fundamental spinor structure, permutation and point-group symmetries, various options for the positive-energy projection procedure are presented. The no-pair Dirac-Coulomb energy converged to a parts-per-billion precision is compared with perturbative results for atomic and molecular systems with small nuclear charge numbers. The subsequent paper [Paper II: D. Ferenc, P. Jeszenszki, and E. M\'atyus (2022)] describes the implementation of the Breit interaction in this framework.

This paper elaborates the integral transformation technique of [K. Pachucki, W. Cencek, and J. Komasa, J. Chem. Phys. 122, 184101 (2005)] and uses it for the case of the non-relativistic kinetic and Coulomb potential energy operators, as well as for the relativistic mass-velocity and Darwin terms. The techniques are tested for the ground electronic state of the helium atom and new results are reported for the ground electronic state of the H$_3^+$ molecular ion near its equilibrium structure.

A variational solution procedure is reported for the many-particle no-pair Dirac-Coulomb-Breit Hamiltonian aiming at a parts-per-billion (ppb) convergence of the atomic and molecular energies, described within the fixed nuclei approximation. The procedure is tested for nuclear charge numbers from $Z=1$ (hydrogen) to $28$ (iron). Already for the lowest $Z$ values, a significant difference is observed from leading-order Foldy-Woythusen perturbation theory, but the observed deviations are smaller than the estimated self-energy and vacuum polarization corrections.

A hyperbolic singularity in the wave-function of $s$-wave interacting atoms is the root problem for any accurate numerical simulation. Here we apply the transcorrelated method, whereby the wave-function singularity is explicitly described by a two-body Jastrow factor, and then folded into the Hamiltonian via a similarity transformation. The resulting non-singular eigenfunctions are approximated by stochastic Fock-space diagonalisation with energy errors scaling with $1/M$ in the number $M$ of single-particle basis functions. The performance of the transcorrelated method is demonstrated on the example of strongly correlated fermions with unitary interactions. The current method provides the most accurate ground state energies so far for three and four fermions in a rectangular box with periodic boundary conditions., Comment: 16 pages, 11 figures; revised after referee comments

When seeking a numerical representation of a quantum-mechanical multiparticle problem it is tempting to replace a singular short-range interaction by a smooth finite-range pseudopotential. Finite basis set expansions, e.g.~in Fock space, are then guaranteed to converge exponentially. The need to faithfully represent the artificial length scale of the pseudopotential, however, places a costly burden on the basis set. Here we discuss scaling relations for the required size of the basis set and demonstrate the basis set convergence on the example of a two-dimensional system of few fermions with short-range $s$-wave interactions in a harmonic trapping potential. In particular we show that the number of harmonic-oscillator basis functions needed to reach a regime of exponential convergence for a Gaussian pseudopotential scales with the fourth power of the pseudopotential length scale, which can be improved to quadratic scaling when the basis functions are re-scaled appropriately. Numerical examples for three fermions with up to a few hundred single-particle basis functions are presented and implications for the feasibility of accurate numerical multi-particle simulations of interacting ultra-cold atom systems are discussed., Comment: 11 pages, 2 figures

Exact diagonalization expansions of Bose or Fermi gases with contact interactions converge very slowly due to a non-analytic cusp in the wave function. Here we develop a transcorrelated approach where the cusp is treated exactly and folded into the many-body Hamiltonian with a similarity transformation that removes the leading order singularity. The resulting transcorrelated Hamiltonian is not hermitian but can be treated numerically with a standard projection approach. The smoothness of the wave function improves by at least one order and thus the convergence rate for the ground state energy improves. By numerical investigation of a one-dimensional gas of spin-$\frac{1}{2}$ fermions we find the error in the transcorrelated energy to scale as $M^{-3}$ with a single-particle basis of $M$ plane waves compared to $M^{-1}$ for the expansion of the original Hamiltonian and $M^{-2}$ using conventional lattice renormalization.

We provide accurate expressions for the $s$-wave scattering length for a Gaussian potential well in one, two and three spatial dimensions. The Gaussian potential is widely used as a pseudopotential in the theoretical description of ultracold atomic gases, where the $s$-wave scattering length is a physically relevant parameter. We first describe a numerical procedure to compute the value of the $s$-wave scattering length from the parameters of the Gaussian but find that its accuracy is limited in the vicinity of singularities that result from the formation of new bound states. We then derive simple analytical expressions that capture the correct asymptotic behavior of the $s$-wave scattering length near the bound states. Expressions that are increasingly accurate in wide parameter regimes are found by a hierarchy of approximations that capture an increasing number of bound states. The small number of numerical coefficients that enter these expressions is determined from accurate numerical calculations. The approximate formulas combine the advantages of the numerical and approximate expressions, yielding an accurate and simple description from the weakly to the strongly interacting limit., Comment: 13 pages, 6 figures