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Compactifying the Electronic Wavefunction II: Quantum Estimators for Spin-Coupled Generalized Valence Bond Wavefunctions Applied to H4

Quantum Physics 2026-04-20 v2 Strongly Correlated Electrons Chemical Physics

Abstract

Valence-bond-based wavefunctions, such as the spin-coupled generalized valence bond (SCGVB) ansatz, provide compact and chemically interpretable descriptions of strong correlation. However, their non-orthogonal determinant structure poses a major challenge for quantum computing implementations. Although recent fermion-qubit mappings allow non-orthogonal orbitals to be encoded on qubit registers, the evaluation of overlap and Hamiltonian matrix elements remains a bottleneck on NISQ devices due to the need for ancilla qubits, controlled operations, and deep circuits. We present a measurement-driven quantum framework for evaluating these quantities in SCGVB wavefunctions. Instead of preparing the full wavefunction, we reformulate the problem in terms of vacuum expectation values of Pauli-string operators, enabling evaluation with shallow, ancilla-free circuits based on local Clifford rotations and computational-basis measurements. Unlike Hadamard-test-based approaches, this method avoids controlled operations by reducing the task to local Pauli measurements, yielding a low-depth strategy suitable for near-term devices. We demonstrate the framework on the H4 cluster along a dissociation pathway from square geometry to the separated-fragment limit, considering five nuclear configurations via quantum-circuit emulation. The overlap and Hamiltonian matrices agree well with classical Lowdin-based references, and Chirgwin-Coulson weights remain chemically consistent. These results highlight the robustness of the approach and its suitability as a NISQ-compatible building block for SCGVB-based quantum algorithms.

Keywords

Cite

@article{arxiv.2603.12045,
  title  = {Compactifying the Electronic Wavefunction II: Quantum Estimators for Spin-Coupled Generalized Valence Bond Wavefunctions Applied to H4},
  author = {Bruna Gabrielly},
  journal= {arXiv preprint arXiv:2603.12045},
  year   = {2026}
}
R2 v1 2026-07-01T11:16:56.928Z