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.

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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

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article

State-averaged quantum algorithms for multiconfigurational surface chemistry: A benchmark on Rh@TiO2(110)

Peter Reinholdt, Ernst D. Larsson, Jacob Kongsted, Erik Kjellgren
The Journal of Chemical Physics
Machine Learning in Materials Science
article

State-averaged quantum algorithms for multiconfigurational surface chemistry: A benchmark on Rh@TiO2(110)

Peter Reinholdt, Ernst D. Larsson, Jacob Kongsted, Erik Kjellgren
article en

Abstract

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.

The Journal of Chemical PhysicsVol. 165(8)
University of Southern Denmark (DK)
Danish e-Infrastructure Cooperation, Novo Nordisk Fonden
Openalex Percentile: Top 73%
Machine Learning in Materials Science
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