Forensic SCF-Reference Validation of the LLZO Pressure-Sweep Record: Widespread Multi-Root Contamination and Scope Correction Verdict (read first) Not decision-grade as originally framed: the LLZO pressure-sweep headline claims — the monotonic Li-present σ-stabilisation trend, the d⁰ "bifurcation" interpretation, and the pressure-inversion narrative — are not supported by the current evidence, because the arms required to support them show severe SCF reference-root instability large enough to explain the apparent σ/basin/IBG structure. Survives the first screen (exact-reference validation still pending): P3_Li1 and P4_Li1 pass the SCF-root stability check at N=20. P4_Li0 passes a targeted N=20 rerun, though an earlier full-sweep run showed minor spurious-root contamination; it is retained as a cleaner Li-vacancy endpoint candidate, root-filter / exact-reference validation pending. P3_Li1 (stable reference, published σ ≈ 14.14 kcal/mol) is the strongest remaining anomaly candidate. Unsupported pending reruns (not refuted): the d⁰-bifurcation and pressure-inversion interpretations are withdrawn as decision-grade claims until root-pinned or physical-root-filtered reconstructions are performed. This work does not assert that a correctly-converged calculation would be featureless. Methods finding: the same SCF reference-multiplicity failure mode characterised in the Fe₄N₂ correction (Zenodo 10.5281/zenodo.20264767) is present, and more widespread, in this LLZO sweep. It is documented here as a citable hazard for σ-based electronic-landscape diagnostics. This is a corrected, superseding version of an earlier deposit. The previous version ("What Happens Inside a Solid-State Battery Electrolyte Under Pressure — A Quantum Ensemble Study") reported a pressure-driven electronic-landscape inversion, a monotonic Li-present stabilisation trend, and an unexpected d⁰ Zr⁴⁺ bifurcation in LLZO. A forensic validation applying the methodology developed for the Fe₄N₂ correction shows that most of the arms underpinning those claims suffer SCF reference-root contamination. The headline interpretations are withdrawn as decision-grade results. What survives, the limitations, and the methods finding are stated explicitly below. 1. Background and what the original deposit claimed LLZO (Li₇La₃Zr₂O₁₂) is a leading solid-state-battery electrolyte. The original deposit ran a VQE ensemble "electronic-landscape" study on a Zr–O₄(–Li) cluster model (10e,10o, 20 qubits, UCCSD/COBYLA, LANL2DZ/6-31G) across five compression amplitudes (B0→P4) and two lithiation states (Li-present singlet, charge 0; Li-vacancy doublet, charge +1), 15 seeds per arm. It reported, as physical findings: A monotonic Li-present stabilisation trend: σ decreasing from 34.25 (B0_Li1) to 3.94 kcal/mol (P4_Li1). A pressure-driven inversion: Li-vacancy σ rising (2.57 → 6.23) while Li-present σ falls, crossing over at P4. An unexpected d⁰ bifurcation: 2–3 electronic basins with inter-basin gaps up to 47.7 kcal/mol in a formal closed-shell Zr⁴⁺ singlet, "warranting mechanistic investigation," supported by an N=35 confirmation run. These were positioned as actionable (pre-synthesis dopant ranking) and as cross-material validation of the diagnostic. 2. What the validation found The same forensic method that corrected the Fe₄N₂ deposit was applied: each arm's cluster Hamiltonian was rebuilt N=20 times from the engine's own registered LLZO geometry and configuration (geometry keys and charge/spin read from source, not assumed), and the per-build Hartree–Fock energy was clustered to detect SCF reference-root multiplicity. The diagnostic-relevant quantity is whether the SCF converges to a single physical reference across seeds, or jumps among multiple roots — in which case the published σ measures root-jumping, not an electronic landscape. 2.1 Per-arm SCF-root stability (N = 20) Arm Published σ (kcal/mol) Full HF spread (kcal/mol) Physical-root HF spread (kcal/mol) Spurious / N Classification B0_Li1 34.25 116–123 (two N=20 runs) 0.000 19/20 (both runs) Contaminated P1_Li1 30.62 38.75 0.0004 15–16/20 Contaminated P2_Li1 27.75 36.44 0.0005 11–15/20 Contaminated P1_Li0 1.19 195.71 0.057 6/20 Contaminated B0_Li0 2.57 1.26 0.054 7/20 Contaminated P2_Li0 3.63 1.14 0.089 3/20 Contaminated P3_Li0 5.42 1.60 0.019 1/20 Minor spurious root P4_Li0 6.23 0.014 (targeted rerun); 1.37 (earlier full sweep) 0.014 0/20 (rerun); 2/20 (earlier) Cleaner endpoint, caveated P3_Li1 14.14 0.00012 0.00012 0/20 Root-stable P4_Li1 3.94 0.0005 0.0005 0/20 Root-stable (Values from the N=20 validation JSONs 20260518T192547Z, 20260519T012507Z, 20260519T013353Z, 20260519T030019Z, bundled with this record. Where two independent N=20 runs exist for an arm — B0/P1/P2_Li1 — the contamination is reproduced in both, with the spurious-root fraction varying run-to-run as expected for a stochastic spurious root; the presence and magnitude of contamination are reproducible. P3_Li1 and P4_Li1 are root-stable across two independent N=20 runs each, agreeing to the fourth decimal.) 2.2 What this means for the headline claims The decisive observation: every contaminated arm has a physical-root HF spread of ≤ 0.10 kcal/mol — when the SCF reaches the correct reference it converges tightly. The large full spreads (36–196 kcal/mol) are produced by inconsistent convergence among distinct SCF roots — in some arms (e.g. P2_Li0, P3_Li0) the spurious root is the minority outcome, in others (e.g. B0_Li1, P1_Li1) the physical root is the minority outcome. Therefore, for the contaminated arms, the published σ is not a measure of an electronic landscape; it reflects the frequency and magnitude of SCF reference-root jumping across the seed ensemble. This directly undermines the headline interpretations: Monotonic Li-present stabilisation (σ 34.25 → 3.94). Its high-σ end — B0_Li1 (19/20 spurious, 123 kcal/mol full spread), P1_Li1 and P2_Li1 (15/20 spurious, ~37 kcal/mol) — is reference-contaminated. The apparent "stabilisation" largely tracks the spurious-root contribution diminishing toward higher compression, not a physical ordering of the electronic landscape. The trend is not decision-grade as published. The d⁰ "bifurcation". The published d⁰ bifurcation interpretation is not supported by the current evidence, because the corresponding arms (B0/P1/P2_Li1) show SCF reference instability large enough to explain the apparent multi-basin structure. The contaminated evidence does not support overriding the expected electronic rigidity of a formal d⁰ Zr⁴⁺ centre; the reported "2–3 basins, IBG up to 47.7 kcal/mol" coincide in magnitude with the measured spurious-root separations. The N=35 confirmation established that the scatter is reproducible, which — as in the Fe₄N₂ case — confirms an artifact is reproducible, not that the structure is physical. This is stated as unsupported pending root-pinned reruns, not as a definitive claim that the corrected calculation would be featureless. The pressure inversion. The inversion requires both the Li-present and Li-vacancy σ trends to be physical. The Li-present high-σ points are contaminated; on the Li-vacancy side B0_Li0 (7/20 spurious) and P1_Li0 (6/20, 196 kcal/mol full spread) are also contaminated. The crossover endpoints are individually the cleanest arms (P4_Li1 root-stable; P4_Li0 clean on a targeted rerun, caveated), but the trends leading to the crossover run through contaminated references on both sides. The inversion narrative is withdrawn as a decision-grade claim pending reconstruction on root-pinned references. 3. What survives Two arms cleanly pass the SCF-root stability screen at N=20 across independent runs (P3_Li1, P4_Li1); a third (P4_Li0) passes a targeted rerun with a caveat: Arm Published σ Status P3_Li1 14.14 kcal/mol Root-stable (0/20 spurious, two independent N=20 runs). Strongest remaining anomaly candidate — stable reference with a non-trivial published σ. P4_Li1 3.94 kcal/mol Root-stable. Low σ; the stabilised endpoint of the (now-withdrawn) trend. P4_Li0 6.23 kcal/mol Passes a targeted N=20 rerun (0/20 spurious); an earlier full-sweep run showed minor spurious-root contamination. Retained as a cleaner Li-vacancy endpoint candidate, validation pending. P3_Li1 is the scientifically important survivor: a stable SCF reference with a published σ ≈ 14 kcal/mol means the ruggedness there is not a root-jump artifact. Whether that σ is a genuine VQE-landscape feature or a VQE-optimiser pathology on top of a stable Hamiltonian cannot be settled by the SCF-root screen alone and requires an independent same-active-space exact reference (see Limitations). P3_Li1 is therefore reported as surviving the first screen, exact-reference validation pending — not as a corrected physical result. 4. The methods finding This LLZO sweep exhibits the same SCF reference-multiplicity failure mode characterised in the Fe₄N₂ correction (Zenodo 10.5281/zenodo.20264767), and more pervasively: 7 of 10 arms are contaminated, with spurious-root frequencies from 5% to 95% and spurious-root separations up to ~196 kcal/mol. The transferable lesson, consistent across both records: σ-based "electronic-landscape" diagnostics built on unconstrained SCF references can report physics-shaped artifacts; an SCF-root stability screen and an independent same-Hamiltonian exact reference are prerequisites, not optional checks. Documenting this failure mode, with the per-arm contamination quantified, is the substantive contribution of this corrected version. 5. Limitations and honest scope The SCF-root screen rules out one specific artifact (reference multiplicity). A UNIMODAL_STABLE arm has a well-defined reference but its published σ has not thereby been validated as physical: distinguishing a genuine rugged VQE landscape from VQE-optimiser pathology on a stable Hamiltonian requires an independent in-sector exact reference. That solver (memory-safe for the large singlet sector — the dense path is intractable, ≈64 GB for the (10e,10o, 2Sz=0) sector) is not yet run; it is the planned next step and a future version of this record. Accordingly, P3_Li1/P4_Li1/P4_Li0 are reported as surviving the SCF screen only. None is asserted as a confirmed physical result. The d⁰-bifurcation and pressure-inversion interpretations are unsupported pending reruns, explicitly not refuted. A root-pinned or physical-root-filtered reconstruction could in principle recover structure; this work does not exclude that, it only shows the original evidence is contaminated. The original deposit's actionable claims (pre-synthesis dopant ranking, cross-material mechanism confirmation) inherit the contamination of the arms they rest on and should not be relied upon pending the above reruns. 6. Files in this deposit File Contents llzo_validation_20260518T192547Z.json Full 10-arm SCF-root screen, N=20. Primary evidence for §2.1. llzo_validation_20260519T012507Z.json Independent re-run, contaminated Li-present arms (B0/P1/P2_Li1), N=20. llzo_validation_20260519T013353Z.json Li-vacancy arms (B0/P3/P4_Li0), N=20. llzo_validation_20260519T030019Z.json Li-vacancy + survivor re-run (P1/P2_Li0, P3/P4_Li1), N=20. llzo_validation_20260518T204304Z.json Survivor confirmation (P3_Li1, P4_Li1), independent run. llzo_validation_20260518T192450Z.json Early N=3 screen (B0 arms); superseded by N=20 runs, included for completeness. Original-record files (carried over) llzo_pressure_sweep.csv, llzo_basin_confirm_n35.csv, llzo_dopant_sweep_v5.csv, and the original .docx files — retained so the superseded numbers remain inspectable against this correction. Each JSON records per-build HF energies, physical/spurious clustering, charge/spin/geometry provenance (read from the engine source, not assumed), and a self-contained summary. The proprietary VQE engine is not included (consistent with the Fe₄N₂ deposit); this record provides the validation artifacts, not a standalone re-runnable engine. 7. Citation and supersession This version supersedes and corrects the prior deposit. The prior version's pressure-inversion, monotonic-stabilisation, and d⁰-bifurcation conclusions should not be cited or relied upon. This version should be cited for: (a) the forensic SCF-reference validation and the per-arm contamination characterisation, (b) the documented cross-record SCF reference-multiplicity failure mode (with Zenodo 10.5281/zenodo.20264767), and (c) P3_Li1 as a surviving anomaly candidate pending independent exact-reference validation.