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arxiv: 2606.23538 · v1 · pith:HMQTZ6LJnew · submitted 2026-06-22 · 🪐 quant-ph · physics.atom-ph

Structure and information measures of few-electron systems under a spherically symmetric Gaussian potential within a density functional approach

Pith reviewed 2026-06-26 08:23 UTC · model grok-4.3

classification 🪐 quant-ph physics.atom-ph
keywords density functional theoryGaussian potentialShannon entropyFisher informationelectron correlationfew-electron systemsCollin's conjecturequantum dots
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The pith

Gaussian potential parameters control atomic energies and produce a non-linear loop in the Fisher-Shannon plane that signals weakened electron correlation.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper applies density functional theory to few-electron systems placed inside a spherically symmetric Gaussian potential, solving the radial Kohn-Sham equation with a work-function exchange potential plus Wigner and Lee-Yang-Parr correlation functionals. Numerical results obtained via the generalized pseudospectral method show that narrowing the potential width raises total energy, drives position-space Shannon entropy through a minimum, and pushes momentum-space Shannon entropy and position Fisher information through maxima; deepening the potential amplifies all these trends. The Fisher-Shannon plane constructed from these quantities displays progressive localization and density compression, which the authors interpret as a weakening of relative electron-correlation effects and the appearance of a non-linear loop-like feature in Collin's conjecture.

Core claim

Through density functional calculations on H, He-like ions (Z=2-18), Li, and Be under a Gaussian potential, energies increase with decreasing width and increasing depth of the confining potential. Companion calculations of Shannon entropies and Fisher information reveal that position entropy reaches a minimum while momentum entropy and position Fisher information reach maxima under the same changes; these trends are amplified by greater potential depth. The resulting Fisher-Shannon plane indicates progressive localization together with compression of the electronic density, thereby pointing to a weakening of relative electron-correlation effects and producing a non-linear loop-like feature i

What carries the argument

Fisher-Shannon plane constructed from position and momentum Shannon entropies together with position Fisher information, obtained from Kohn-Sham densities under Gaussian confinement.

If this is right

  • Energy of H, He-like ions, Li, and Be can be raised by reducing the width or increasing the depth of the Gaussian potential.
  • Position-space Shannon entropy reaches a minimum while momentum-space entropy and position Fisher information reach maxima when the Gaussian width decreases.
  • Increasing the depth of the Gaussian potential amplifies the changes in energy and all three information measures.
  • The Fisher-Shannon plane exhibits progressive localization and density compression that the calculation links to weaker relative electron correlation.
  • Collin's conjecture produces a non-linear loop-like feature under the Gaussian confinement.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

  • The same information-measure analysis could be repeated for other smooth confining potentials to test whether the non-linear loop is specific to the Gaussian shape.
  • The observed energy control by potential parameters supplies a concrete route for estimating how confinement alters ionization thresholds in model quantum-dot systems.
  • If the loop persists when the Wigner or LYP functional is replaced by a different correlation approximation, the weakening of relative correlation would be more robust than the specific functionals used here.

Load-bearing premise

The local parameterized Wigner functional and the non-linear LYP functional remain accurate descriptors of electron correlation when the external potential is changed to a spherically symmetric Gaussian form.

What would settle it

Exact numerical solution of the Schrödinger equation for the helium atom in the same Gaussian potential, followed by direct computation of its Fisher-Shannon plane, would show whether the non-linear loop appears or the correlation-weakening trend holds.

Figures

Figures reproduced from arXiv: 2606.23538 by Amlan K. Roy, Raveena Arya, Santanu Mondal.

Figure 1
Figure 1. Figure 1: FIG. 1 [PITH_FULL_IMAGE:figures/full_fig_p005_1.png] view at source ↗
Figure 2
Figure 2. Figure 2: FIG. 2. He 1s2s ( [PITH_FULL_IMAGE:figures/full_fig_p007_2.png] view at source ↗
Figure 3
Figure 3. Figure 3: FIG. 3. The behavior of [PITH_FULL_IMAGE:figures/full_fig_p009_3.png] view at source ↗
Figure 4
Figure 4. Figure 4: FIG. 4. Variation of [PITH_FULL_IMAGE:figures/full_fig_p009_4.png] view at source ↗
Figure 5
Figure 5. Figure 5: FIG. 5. Variation of [PITH_FULL_IMAGE:figures/full_fig_p010_5.png] view at source ↗
Figure 6
Figure 6. Figure 6: FIG. 6. Variation of [PITH_FULL_IMAGE:figures/full_fig_p010_6.png] view at source ↗
Figure 7
Figure 7. Figure 7: FIG. 7. Variation of [PITH_FULL_IMAGE:figures/full_fig_p011_7.png] view at source ↗
Figure 8
Figure 8. Figure 8: FIG. 8. The Fisher-Shannon information plane for He-like [PITH_FULL_IMAGE:figures/full_fig_p011_8.png] view at source ↗
Figure 9
Figure 9. Figure 9: FIG. 9. Variation of [PITH_FULL_IMAGE:figures/full_fig_p012_9.png] view at source ↗
read the original abstract

Energies of H, He-like ($Z=2-18$) ions, Li, and Be are investigated under a spherically symmetric Gaussian potential through a density functional formalism. The radial Kohn-Sham equation has been solved by invoking a work function-based exchange potential. The effect of electron correlation is analyzed by incorporating two functionals: a local parameterized Wigner functional and a non-linear gradient- and Laplacian-dependent Lee-Yang-Parr (LYP) functional. The generalized pseudospectral method is employed to provide accurate numerical eigenfunctions and eigenvalues. This allows nonuniform, optimal spatial discretization fulfilling the Dirichlet boundary conditions. This work demonstrates a possible manipulation of energy by controlling dot parameters. Apart from ground states, exploratory results are also reported for low-lying excited state $1s2s$ ($^{1,3}S$) of He atom. Companion calculations are also performed for various information-theoretic measures, such as Shannon entropy in position ($S_{r}$), momentum ($S_{p}$) spaces, and Fisher information in position space ($I_{r}$). The behavior of correlation functionals in presence of Gaussian potential is examined critically. We find that energy increases, $S_{r}$ exhibits minima, while $S_{p}$, $I_{r}$ attain maxima for a decrease in the width of potential, whereas an increase in potential depth further amplifies these effects across all properties. The Fisher-Shannon plane reveals a progressive localization as well as the compression of electronic density, and thereby indicates a weakening of relative electron-correlation effects. In the Collin's conjecture, it gives rise to a non-linear loop-like feature. Much of the results are presented here for the first time.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Referee Report

2 major / 1 minor

Summary. The manuscript investigates energies of H, He-like ions (Z=2-18), Li, and Be under a spherically symmetric Gaussian potential using Kohn-Sham DFT. A work-function exchange potential is combined with either a local parameterized Wigner or gradient/Laplacian-dependent LYP correlation functional. The radial KS equation is solved numerically via the generalized pseudospectral method. Trends in total energies, Shannon entropies S_r and S_p, and Fisher information I_r are reported as functions of Gaussian depth and width, along with interpretations of the Fisher-Shannon plane (progressive localization, density compression, weakening relative correlation) and a non-linear loop feature in Collin's conjecture. Exploratory results for He 1s2s (^{1,3}S) excited states are included.

Significance. If the results hold, the work demonstrates how Gaussian confinement parameters can manipulate energies and information measures in few-electron systems, with potential relevance to quantum-dot modeling. The comparison of two correlation functionals under non-Coulombic confinement and the reported loop in Collin's conjecture would constitute a novel contribution to information-theoretic analyses of confined atoms.

major comments (2)
  1. [Abstract and correlation-functional analysis] The central interpretations—that the Fisher-Shannon plane shows progressive localization, density compression, and weakening of relative electron-correlation effects, plus the non-linear loop in Collin's conjecture—rest on the accuracy of the Wigner and LYP functionals for the Gaussian external potential. No cross-validation against exact diagonalization, quantum Monte Carlo, or other benchmarks is reported for this potential form (see abstract and the section examining correlation functionals).
  2. [Methods and results sections] The local parameterized Wigner functional and the non-linear LYP functional were originally constructed and calibrated for Coulombic atoms/ions. Their transferability to a spherically symmetric Gaussian confining potential is invoked without additional validation or adjustment, which is load-bearing for all reported trends in energies, S_r, S_p, and I_r.
minor comments (1)
  1. [Results] The manuscript would benefit from explicit tables or figures presenting numerical values of energies and entropies (with convergence checks) rather than only qualitative trends, to support reproducibility.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for the constructive feedback. We address the two major comments on functional validation and transferability below, offering partial revisions to strengthen the discussion of limitations while preserving the exploratory scope of the work.

read point-by-point responses
  1. Referee: [Abstract and correlation-functional analysis] The central interpretations—that the Fisher-Shannon plane shows progressive localization, density compression, and weakening of relative electron-correlation effects, plus the non-linear loop in Collin's conjecture—rest on the accuracy of the Wigner and LYP functionals for the Gaussian external potential. No cross-validation against exact diagonalization, quantum Monte Carlo, or other benchmarks is reported for this potential form (see abstract and the section examining correlation functionals).

    Authors: We agree that the manuscript reports no direct benchmarks (e.g., exact diagonalization or QMC) for the Gaussian potential. The interpretations are drawn from trends obtained with standard DFT functionals applied to this external potential, and the paper already compares results from two distinct correlation functionals to examine their behavior critically. The focus is on qualitative changes with confinement parameters rather than absolute accuracy. We will revise the abstract, methods, and discussion sections to explicitly qualify the interpretations as approximate, note the absence of such benchmarks, and suggest future validation studies. This constitutes a partial revision. revision: partial

  2. Referee: [Methods and results sections] The local parameterized Wigner functional and the non-linear LYP functional were originally constructed and calibrated for Coulombic atoms/ions. Their transferability to a spherically symmetric Gaussian confining potential is invoked without additional validation or adjustment, which is load-bearing for all reported trends in energies, S_r, S_p, and I_r.

    Authors: The Wigner and LYP functionals are applied in their published forms, as is common when extending DFT to non-Coulombic confinements such as quantum dots. The manuscript already contrasts the two functionals to highlight differences and consistencies in trends. We acknowledge that explicit validation or reparameterization for the Gaussian case is absent. We will add a dedicated paragraph in the methods section discussing the transferability assumption, citing prior DFT applications to confined systems, and noting this as a limitation. This is a partial revision. revision: partial

Circularity Check

0 steps flagged

No circularity: direct numerical DFT computation of energies and information measures

full rationale

The paper solves the radial Kohn-Sham equation numerically via the generalized pseudospectral method using a work-function exchange potential plus standard literature correlation functionals (parameterized Wigner and LYP). Energies, Shannon entropies S_r/S_p, Fisher information I_r, and the Fisher-Shannon plane are obtained directly as outputs of these orbitals and densities. No parameters are fitted to the reported quantities and then relabeled as predictions; no self-citation chain supplies a load-bearing uniqueness theorem or ansatz; the derivation chain consists of standard DFT steps whose results are independent of the target observables by construction.

Axiom & Free-Parameter Ledger

2 free parameters · 2 axioms · 0 invented entities

The paper relies on the standard Kohn-Sham DFT framework and two established correlation functionals whose parameters originate outside this work. No new entities are postulated. The Gaussian potential parameters are varied for exploration rather than fitted to produce the central claims.

free parameters (2)
  • Gaussian potential depth and width
    Exploratory parameters varied to map trends; not derived or fitted to the reported observables.
  • Wigner functional parameters
    Parameterized form taken from prior literature and used without re-fitting in this study.
axioms (2)
  • domain assumption Kohn-Sham DFT with the chosen exchange and correlation functionals is adequate for these confined systems
    Invoked as the computational framework without derivation or error analysis in the abstract.
  • domain assumption Generalized pseudospectral method yields numerically exact eigenfunctions and eigenvalues under the stated boundary conditions
    Stated as the solution technique without convergence data.

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