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Orbital-Optimized Unitary Coupled Cluster for Indirect Nuclear Spin-Spin Coupling Constants within a Quantum Linear Response Framework

Chemical Physics 2025-11-27 v2 Quantum Physics

Abstract

We present a quantum linear response (qLR) approach within an active-space framework for computing indirect nuclear spin-spin coupling constants, a key ingredient in NMR spectra predictions. The method employs the unitary coupled cluster (UCC) ansatz and its orbital-optimized variant (ooUCC), both suitable for quantum computing implementations, to evaluate spin-spin coupling constants via qLR. Test calculations on five small molecules are compared with CASCI, CASSCF, and conventional CCSD results. qLR with UCC/ooUCC yields spin-spin coupling constants comparable to classical methods. We further examine the role of orbital optimization and find that ooUCC markedly affects the computed couplings; orbital-optimized results show better agreement with CCSD. These findings indicate that orbital optimization is important for accurate NMR coupling predictions within quantum-computing-friendly correlated methods.

Keywords

Cite

@article{arxiv.2511.09730,
  title  = {Orbital-Optimized Unitary Coupled Cluster for Indirect Nuclear Spin-Spin Coupling Constants within a Quantum Linear Response Framework},
  author = {Juliane H. Fuglsbjerg and Peter Reinholdt and Erik Kjellgren and Phillip W. K. Jensen and Sonia Coriani and Jacob Kongsted and Stephan P. A. Sauer},
  journal= {arXiv preprint arXiv:2511.09730},
  year   = {2025}
}

Comments

27 pages, 13 figures

R2 v1 2026-07-01T07:34:39.898Z