arXiv subjects

Péter Jeszenszki

Publications and source records attributed to Péter Jeszenszki.

15 recordsLinked to original sources

arXiv2026

Rovibrational computations for the He$_2$ a $^3Σ_\mathrm{u}^+$ state including non-adiabatic, relativistic, and QED corrections

A potential energy curve (PEC) accurate to a fraction of 1 ppm ($1:10^6$) is computed for the $^3Σ_\mathrm{u}^+$ state of He$_2$ endowed with relativistic and QED corrections. The nuclear Schrödinger equation is solved on this PEC with diagonal Born-Oppenheimer and non-adiabatic mass corrections to obtain highly accurate rotational-vibrational levels. The computed rovibrational intervals and fine-structure splittings, spanning over several orders of magnitude in energy, are found to be in remarkable agreement with available high-resolution spectroscopy data.

physics.chem-ph↗

arXiv2025

Double-pair Coulomb and Breit photon correction to the correlated relativistic energy

The simplest, algebraic quantum-electrodynamical corrections, due to the double-negative energy subspace and instantaneous interactions, are computed to the no-pair energy of two-spin-1/2-fermion systems. Numerical results are reported for two-electron atoms with a clamped nucleus and positronium-like genuine two-particle systems. The Bethe-Salpeter equation provides the theoretical framework, and numerical methods have been developed for its equal-time time-slice. In practice, it requires solving a sixteen-component eigenvalue equation with a two-particle Dirac Hamiltonian, including the appropriate interaction. The double-pair corrections can either be included in the interaction part of the eigenvalue equation or treated as a perturbation to the no-pair Hamiltonian. The numerical results have an $α$ fine-structure constant dependence that is in excellent agreement with the known $α^3E_\mathrm{h}\$-order double-pair correction of non-relativistic quantum electrodynamics.

physics.chem-ph↗

arXiv2025

Spin-dependent terms of the Breit-Pauli Hamiltonian evaluated with an explicitly correlated Gaussian basis set for molecular computations

This work collects the spin-dependent leading-order relativistic and quantum-electrodynamical corrections for the electronic structure of atoms and molecules within the non-relativistic quantum electrodynamics framework. We report the computation of perturbative corrections using an explicitly correlated Gaussian basis set, which allows high-precision computations for few-electron systems. In addition to numerical tests for triplet Be, triplet H$_2$, and triplet H$_3^+$ states and comparison with no-pair Dirac-Coulomb-Breit Hamiltonian energies, numerical results are reported for electronically excited states of the helium dimer, He$_2$, for which the present implementation delivers high-precision magnetic coupling curves necessary for a quantitative understanding of the fine structure of its high-resolution rovibronic spectrum.

physics.chem-ph↗

arXiv2025

High-Precision Quantum Dynamics of He$_2$ over the b $^3Π_\mathrm{g}$-c $^3Σ_\mathrm{g}^+$ Electronic Subspace by including Non-adiabatic, Relativistic and QED Corrections and Couplings

Relativistic, quantum electrodynamics, as well as non-adiabatic corrections and couplings, are computed for the b $^3Π_\mathrm{g}$ and c $^3Σ_\mathrm{g}^+$ electronic states of the helium dimer. The underlying Born-Oppenheimer potential energy curves are converged to 1 ppm ($1:10^6$) relative precision using a variational explicitly correlated Gaussian approach. The quantum nuclear motion is computed over the b $^3Π_\mathrm{g}$-c $^3Σ_\mathrm{g}^+$ (and B $^1Π_\mathrm{g}$-C $^1Σ_\mathrm{g}^+$) 9-(12-)dimensional electronic-spin subspace coupled by non-adiabatic and relativistic (magnetic) interactions. The electron's anomalous magnetic moment is also included; its effect is expected to be visible in high-resolution experiments. The computed rovibronic energy intervals are in excellent agreement with available high-resolution spectroscopy data, including the rovibronic b $^3Π_\mathrm{g}$-state fine structure. Fine-structure splittings are also predicted for the c $^3Σ_\mathrm{g}^+$ levels, which have not been fully resolved experimentally, yet.

physics.chem-ph↗

arXiv2024

One-particle operator representation over two-particle basis sets for relativistic QED computations

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.

physics.chem-ph↗

arXiv2023

The Bethe-Salpeter QED wave equation for bound-state computations of atoms and molecules

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.

physics.chem-ph↗

arXiv2023

Relativistic two-electron atomic and molecular energies using $LS$ coupling and double groups: role of the triplet contributions to singlet states

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 $X\ ^1Σ_\text{g}^+$ 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 $α$ fine-structure constant dependence of the triplet sector contribution to the variational energy is $α^4E_\text{h}$ at leading order, in agreement with the formal perturbation theory result available from the literature.

physics.atom-ph↗

arXiv2022

Variational versus perturbative relativistic energies for small and light atomic and molecular systems

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 $α$ fine-structure constant. The analysis of the polynomial $α$ 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 $α$ dependence of the no-pair DCB energy shows that the higher-order ($α^4 E_\mathrm{h}$) non-radiative QED correction is 5 % of the leading-order ($α^3 E_\mathrm{h}$) 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.

physics.chem-ph↗

arXiv2022

Variational Dirac-Coulomb explicitly correlated computations for atoms and molecules

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. Mátyus (2022)] describes the implementation of the Breit interaction in this framework.

physics.chem-ph↗

arXiv2022

On the Breit interaction in an explicitly correlated variational Dirac-Coulomb framework

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. Mátyus (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.

physics.chem-ph↗

arXiv2021

On the inclusion of cusp effects in expectation values with explicitly correlated Gaussians

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.

physics.chem-ph↗

arXiv2021

All-order relativistic computations for atoms and molecules using an explicitly correlated Gaussian basis

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.

quant-ph↗

arXiv2020

Eliminating the wave function singularity for ultracold atoms by similarity transformation

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.

cond-mat.quant-gas↗

arXiv2019

Are smooth pseudopotentials a good choice for representing short-range interactions?

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.

cond-mat.quant-gas↗

arXiv2018

Accelerating the convergence of exact diagonalization with the transcorrelated method: Quantum gas in one dimension with contact interactions

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.

cond-mat.quant-gas↗