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Physical Review A

Relativistic corrections to the ground-state energy of the positronium molecule

Sergiy Bubin, Monika Stanke, Dariusz Kędziera, Ludwik Adamowicz

Published Jun 11, 2007• 28 citations
Publisher

Abstract

The leading-order relativistic corrections to the ground-state energy of the positronium molecule $({\mathrm{Ps}}_{2})$ have been computed within the framework of perturbation theory. As the zero-order wave function we used a highly accurate nonrelativistic variational expansion in terms of 6000 explicitly correlated Gaussians that yielded the lowest variational upper bound for this system to date. We also report some expectation values representing the properties of ${\mathrm{Ps}}_{2}$.

DOI
10.1103/physreva.75.062504

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quant-pharXiv:2606.24238•Jun 24, 2026
The leading-order relativistic corrections to the ground-state energy of the positronium molecule (Ps2)({\mathrm{Ps}}_{2})(Ps2​) have been computed within the framework of perturbation theory. As the zero-order wave function we used a highly accurate nonrelativistic variational expansion in terms of 6000 explicitly correlated Gaussians that yielded the lowest variational upper bound for this system to date. We also report some expectation values representing the properties of Ps2{\mathrm{Ps}}_{2}Ps2​.
Various geometrical and energetical (bound-state) properties of the positronium negative ion $({\mathrm{Ps}}^{\ensuremath{-}}$ or ${e}^{\ensuremath{-}}{e}^{+}{e}^{\ensuremath{-}})$ are determined by using highly accurate variational wave functions. These wave functions have been constructed by applying the advanced two-stage strategy proposed by Frolov [Phys. Rev. A 57, 2436 (1998)]. The determined total energy of the ground state $E=\ensuremath{-}0.2620050702329757\mathrm{a}.\mathrm{u}.$ is the lowest and most accurate value obtained for this system to date (the corresponding binding energy equals $\ensuremath{-}0.326674721317821\mathrm{eV}).$ The computation of the second-order relativistic corrections $(\ensuremath{\simeq}{\ensuremath{\alpha}}^{2})$ to the total energy is discussed also. The general form of the Breit-Pauli Hamiltonian in the relative coordinates for the ${\mathrm{Ps}}^{\ensuremath{-}}$ ion is presented.
We report a theoretical calculation of the relativistic corrections to the binding energy of positronic alkali-metal atoms. The ground state for the positronic alkali-metal atom is a loosely bound state with the structure of an alkali-metal ion surrounded by a positronium cloud. The correlation between the valence electron and positron in the field of a residual core ion is taken into account using a three-body model. Relativistic corrections to the binding energy for positronic alkali-metal atoms are evaluated based on the Breit-Pauli perturbation theory up to the second order of the fine structure constant. The relativistic corrections caused by the interaction between the valence electron and core ion was evaluated from the decomposed expectation values of the perturbation Hamiltonian. We found that the importance of relativistic corrections to the binding energy, namely the ratio of the net relativistic correction in the total binding energy, is remarkably enhanced in the loosely bound states of positronic alkali-metal atoms, where the charge of the valence electron is screened by the positron as positronium in the outermost region, while the electron is released from the positron near the nucleus. The results imply that positronic atoms with a dominant positronium can serve as an apt testing ground for relativistic quantum mechanics.
The fully correlated calculations in Hylleraas coordinates for the nonrelativistic ground-state energy and the first three S-wave resonances of positronium hydride are reported. For the resonances, the positions and widths are determined using the method of complex-coordinate rotation. Our results significantly improve previous work. For example, the ground-state energy is about five parts in 109{10}^{9}109 in accuracy, the lowest variational upper bound reported to date. A comparison with other previous work is made.
The molecular dipole moment and magnetic hyperfine-structure constant demand an accurate wave function far from the nucleus and in the near nuclear region, respectively. We, therefore, employ the so-called Z-vector method in the domain of relativistic-coupled-cluster theory to calculate the first-order property of molecular systems in their open-shell ground-state configuration. The implemented method is applied to calculate the molecular dipole moment and parallel component of the magnetic hyperfine-structure constant of the SrF molecule. The results of our calculation are compared with the experimental and other available theoretically calculated values. We are successful in achieving good accordance with the experimental results. The result of our calculation of the molecular dipole moment is in the accuracy of $\ensuremath{\sim}0.5$%, which is clearly an improvement over the previous calculation based on the expectation value method in the four-component coupled-cluster framework [V. S. Prasannaa et al., Phys. Rev. A 90, 052507 (2014)]. Thus, it can be inferred that the Z-vector method can provide an accurate wave function in both the near and far nuclear region, which is evident from our calculated results.
In this work, the ground-state energy of the lithium atom is systematically investigated using both time-independent perturbation theory and the variational method to provide a comprehensive pedagogical analysis of many-body atomic systems. The unperturbed Hamiltonian is initially constructed by neglecting electron-electron interactions, treating the system as three independent hydrogen-like electrons to yield a zeroth-order energy baseline of -275.51 eV. The antisymmetric fermionic nature of the exact wave function is rigorously enforced through the Slater determinant formalism. First-order perturbation theory is applied to evaluate static inter-electronic repulsion using exact Coulomb and exchange integrals, refining the energy state to -192.01 eV. To account for dynamical electronic correlation, second-order perturbation theory is computed numerically for virtual single-electron s-orbital transitions, leading to a total perturbative energy of -196.36 eV. A brief discussion of two-electron excitations is also included to encapsulate further physical realism within the framework. Furthermore, a non-orthogonal two-parameter variational approach is employed to model the shell-specific shielding effect. By optimizing the effective nuclear charges, the variational method establishes a superior upper bound energy of -201.187 eV. The results of both methods are comprehensively contrasted against each other and the reference baseline to provide critical insights into the nature of electron correlation and screening in multi-electron atoms.