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arXiv:1809.09023 · Physical Review A

Deciphering the coalescence behavior of Coulomb-Schrödinger atomic wave functions from an operator-product expansion

Y. S. Huang, Yu Jia, Rui Yu

Published Mar 19, 2025• 1 citation
arXivHTMLPDF

Abstract

We revisit the coalescence behavior of the atomic Schr\"odinger wave functions from the angle of an operator-product expansion (OPE) within the nonrelativistic Coulomb-Schr\"odinger effective-field theory. We take the electron-nucleus coalescence as an explicit example to demonstrate our formalism, by proving an exact OPE relation to all orders in perturbation theory. As a consequence, the celebrated Kato's cusp condition can be readily reproduced. Our approach can be readily extended to ascertain the multiparticle coalescence behaviors of atomic wave functions, which are otherwise difficult to achieve from the conventional Schr\"odinger equation approach. Moreover, by incorporating relativistic effects, our OPE approach appears to be able to provide key insight for solving a 90-year-old puzzle concerning the peculiar coalescence behavior of the wave function for a Dirac hydrogen atom.

DOI
10.1103/physreva.111.032814

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We revisit the coalescence behavior of the atomic Schr"odinger wave functions from the angle of an operator-product expansion (OPE) within the nonrelativistic Coulomb-Schr"odinger effective-field theory. We take the electron-nucleus coalescence as an explicit example to demonstrate our formalism, by proving an exact OPE relation to all orders in perturbation theory. As a consequence, the celebrated Kato's cusp condition can be readily reproduced. Our approach can be readily extended to ascertain the multiparticle coalescence behaviors of atomic wave functions, which are otherwise difficult to achieve from the conventional Schr"odinger equation approach. Moreover, by incorporating relativistic effects, our OPE approach appears to be able to provide key insight for solving a 90-year-old puzzle concerning the peculiar coalescence behavior of the wave function for a Dirac hydrogen atom.
Since Kato proved his singularity condition for Coulomb potentials in 1957, there has been interest in the creation of wave functions that meet the prescriptions of the cusp conditions, necessary for high-precision quantum-mechanical calculations. It is well known, that wave-function expansions based on Slater determinants of one-electron functions are poorly convergent with respect to satisfying the electron-electron cusp condition. In this contribution we show that with the wavelet expansion of density operators even the local form of the electron-electron cusp condition is easily representable by Slater determinants of one-electron wavelet functions with a proper asymptotics of the expansion coefficients, which is explicitly calculated for Haar wavelets.
Progress toward the solution of the strongly correlated electron problem has been stymied by the exponential complexity of the wave function. Previous work established an exact two-body exponential product expansion for the ground-state wave function. By developing a reduced density-matrix analog of Dalgarno-Lewis perturbation theory, we prove here that (i) the two-body exponential product expansion is rapidly and globally convergent with each operator representing an order of a renormalized perturbation theory, (ii) the energy of the expansion converges quadratically near the solution, and (iii) the expansion is exact for both ground and excited states. The two-body expansion offers a reduced parametrization of the many-particle wave function as well as the two-particle reduced density matrix with potential applications on both conventional and quantum computers for the study of strongly correlated quantum systems. We demonstrate the result with the exact solution of the contracted Schr\"odinger equation for the molecular chains H4{\mathrm{H}}_{4}H4​ and H5{\mathrm{H}}_{5}H5​.
The form of the wave function at three-electron coalescence points is examined for several spin states using an alternative method to the usual Fock expansion. We find that, in two- and three-dimensional systems, the non-analytical nature of the wave function is characterized by the appearance of logarithmic terms, reminiscent of those that appear as both electrons approach the nucleus of the helium atom. The explicit form of these singularities is given in terms of the interelectronic distances for a doublet and two quartet states of three electrons in a harmonic well.
For one-dimensional many-body systems interacting via the \textit{Coulomb force} and with \textit{arbitrary} external potential energy, we derive (\textit{i}) the \textit{node coalescence condition} for the wave function. This condition rigorously proves the following: (\textit{ii}) that the particles satisfy \textit{only} a node coalescence condition; (\textit{iii}) that irrespective of their charge or statistics, the particles cannot coalesce; (\textit{iv}) that the particles cannot cross each other, and must be ordered; (\textit{v}) the particles are therefore distinguishable; (\textit{vi}) as such their statistics are not significant; (\textit{vii}) conclusions similar to those of the spin-statistics theorem of quantum field theory are arrived at via non-relativistic quantum mechanics; (\textit{viii}) the noninteracting system \textit{cannot} be employed as the lowest-order in a perturbation theory of the interacting system. (\textit{ix}) Finally, the coalescence condition for particles with the short-ranged delta-function interaction and \textit{arbitrary} external potential energy, is also derived. These particles can coalesce and cross each other.
In this paper, some concepts of nonrelativistic many-particle quantum mechanics (e.g., product states, density matrix) are generalized to the relativistic domain using a framework called relativistic Schr\"odinger theory (RST). By using a general ansatz, the RST framework is simplified considerably and some of its field equations are solved directly. The RST approach is then compared with nonrelativistic quantum mechanics (QM) for the case of a product state (conventional QM) and its RST analog. It is shown that relativistic wave equations can be derived from the RST formalism, so that they coincide in the nonrelativistic limit with the well-known Hartree equations.
The associated Laguerre polynomials are very popular in the Schrödinger equation of nonrelativistic quantum mechanics. However, the situation is quite different in the case of the Dirac equation of relativistic quantum mechanics. The exact solutions of the Dirac equation for three-dimensional (3D) hydrogen atom have been obtained using the wavefunction expansion method. The exact solutions of the radial wavefunctions are found in the form of a linear combination of the orthogonal Laguerre basis function spinors. According to the equality of coefficients in Laguerre series on both sides of the equations, the exact eigenenergies and exact expressions of the corresponding eigenstates of the Dirac equation for 3D hydrogen atom are obtained, which are the same as the power series solutions. Additionally, a comparison with the results from Dirac and Schrödinger equations for 3D hydrogen atom is discussed. Due to the relativistic effects, the Dirac bispinor occurs, and there are the tiny differences of the results between Dirac and Schrödinger equations. For the Dirac states with n r = 0, there is one set of the Dirac bispinor. However for the Dirac states with n r ≠ 0, there is a combination of two sets of the Dirac bispinor. For degenerate Dirac states, their exact expansion coefficients are commutative symmetric. These results show that the linear combination of the orthogonal Laguerre basis functions is the exact solutions of the Dirac equation for 3D hydrogen atom.