State-averaged quantum algorithms for multiconfigurational surface chemistry: A benchmark on Rh@TiO2(110)
Accurate modeling of surface catalytic processes often requires methods capable of describing strong correlation, charge transfer, and multiple closely lying electronic states. While density functional theory remains widely used, its limitations for localized electronic states motivate the use of wavefunction-based approaches and, more recently, quantum computing algorithms. However, the performance of quantum Ansätze in chemically motivated, multistate settings remains largely unexplored. Here, we benchmark state-averaged factorized unitary coupled cluster with singles and doubles (SA-fUCCSD) and the adaptive, problem-tailored Ansatz (SA-ADAPT) using an embedded cluster model of NO adsorption on Rh-doped TiO2(110). The system exhibits pronounced multiconfigurational character and multiple state crossings, providing a stringent test. State-averaged CASSCF serves as a reference, and the quantum Ansätze are evaluated as solvers for the corresponding complete active space configuration interaction problem within a fixed orbital basis. We find that SA-fUCCSD improves with increasing circuit depth but requires many parameters and shows sensitivity to initialization. In contrast, SA-ADAPT achieves near-CASSCF accuracy with significantly fewer operators. A modified operator selection scheme, incorporating multiple operators per iteration, substantially accelerates convergence. Our results demonstrate the efficiency of adaptive Ansätze for multistate problems and establish a controlled benchmark for quantum algorithms in chemically motivated systems beyond minimal models.
Authors
- Peter Reinholdt (ORCID: https://orcid.org/0000-0003-2406-700X)
- Ernst D. Larsson (ORCID: https://orcid.org/0000-0001-7655-2993)
- Jacob Kongsted (ORCID: https://orcid.org/0000-0002-7725-2164)
- Erik Kjellgren
Institutions
- University of Southern Denmark (DK)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2026-08-25
- DOI
- https://doi.org/10.1063/5.0339816
- Primary Topic
- Machine Learning in Materials Science
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Danish e-Infrastructure Cooperation
- Novo Nordisk Fonden