What solvable models reveal about Born-Oppenheimer, Born-Huang, and exact factorization

arXiv:2608.08668v2 Announce Type: replace Abstract: The Born-Oppenheimer (BO) and single-surface Born-Huang (BH) approximations replace the full molecular problem by nuclear motion associated with one clamped electronic state, whereas the full BH expansion and exact factorization (EF) are exact representations. We use two analytically transparent models to identify what controls one-surface error. For Fern\'andez's bilinearly coupled oscillators, the Brattsev ground-state bracket was already known; we derive closed-form differences proving strictness for every positive nuclear mass and nonzero stable coupling. Using Hunter's conditional-amplitude construction, we place the closed-form ground-state EF potential alongside BO and single-surface BH. Exact excited-state calculations show that the bracket does not extend through the spectrum. The diagonal BH correction is the quantum-metric coefficient of the retained electronic state divided by twice the nuclear mass. Fern\'andez's sixth-order expansion shows that the next omitted correction contains the same derivative couplings, an additional inverse electronic-energy separation, and a factor depending on the nuclear state. We therefore add a two-state model with a position-dependent gap. Decreasing its minimum separation makes the metric higher and narrower while leaving the total Fubini-Study length equal to pi/2. The exact EF, BO, and BH potentials can differ visibly even when their nuclear ground-state amplitudes are nearly identical. The two models show that one-surface accuracy depends on nuclear mass, electronic-state variation, energy separation from omitted states, and the nuclear wavefunction.

Abstract:The Born-Oppenheimer (BO) and single-surface Born-Huang (BH) approximations replace the full molecular problem by nuclear motion associated with one clamped electronic state, whereas the full BH expansion and exact factorization (EF) are exact representations. We use two analytically transparent models to identify what controls one-surface error. For Fernández's bilinearly coupled oscillators, the Brattsev ground-state bracket was already known; we derive closed-form differences proving strictness for every positive nuclear mass and nonzero stable coupling. Using Hunter's conditional-amplitude construction, we place the closed-form ground-state EF potential alongside BO and single-surface BH. Exact excited-state calculations show that the bracket does not extend through the spectrum. The diagonal BH correction is the quantum-metric coefficient of the retained electronic state divided by twice the nuclear mass. Fernández's sixth-order expansion shows that the next omitted correction contains the same derivative couplings, an additional inverse electronic-energy separation, and a factor depending on the nuclear state. We therefore add a two-state model with a position-dependent gap. Decreasing its minimum separation makes the metric higher and narrower while leaving the total Fubini-Study length equal to pi/2. The exact EF, BO, and BH potentials can differ visibly even when their nuclear ground-state amplitudes are nearly identical. The two models show that one-surface accuracy depends on nuclear mass, electronic-state variation, energy separation from omitted states, and the nuclear wavefunction.

Revised and expanded version; title changed from "Born-Oppenheimer, Born-Huang, and exact factorization: quantum geometry and error in analytically transparent benchmark models." Historical attribution and terminology have been clarified, and the exact and numerical comparisons and error-budget discussion have been strengthened. Main conclusions unchanged. 37 pages, 5 figures, 5 tables

Quantum Physics (quant-ph); Chemical Physics (physics.chem-ph)

arXiv:2608.08668 [quant-ph]

(or arXiv:2608.08668v2 [quant-ph] for this version)

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What solvable models reveal about Born-Oppenheimer, Born-Huang, and exact factorization

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