In this study, we analyze the choice of local unitary cluster Jastrow (LUCJ) ansatz initialization and sensitivity of the sample-based quantum diagonalization (SQD) algorithm within the quantum-centric supercomputing (QCSC) framework. We examine six initialization strategies, including those based on coupled-cluster singles and doubles (CCSD), Møller-Plesset second-order perturbation theory (MP2), data-driven coupled-cluster (DDCC), and trivial (zeroes and random) initializations, across twelve molecular systems and three basis sets (STO-3G, cc-pVDZ, and aug-cc-pVDZ). We find that while the mean absolute percentage errors (MAPEs) between the alternative and CCSD-initialized t2-amplitudes span many orders of magnitude, the resulting SQD energies are largely insensitive to this variation. In particular, most initializations recover energies within chemical accuracy (+/-1.6 mEh) of the CCSD reference, with convergence improving as the basis set size increases. Notably, random initialization achieves performance competitive with CCSD across all basis sets, while zeroes initialization, despite having smaller deviations from CCSD, yields the worst energy agreement. Our results highlight that the proximity to the CCSD initialization is not a reliable predictor of the quality of electronic energies. These findings establish that configuration recovery within SQD, rather than circuit initialization, is the dominant factor governing energy accuracy, and suggest that computationally cheaper initialization strategies are viable alternatives to CCSD for QCSC workflows
In this study, we analyze the choice of local unitary cluster Jastrow (LUCJ) ansatz initialization and sensitivity of the sample-based quantum diagonalization (SQD) algorithm within the quantum-centric supercomputing (QCSC) framework. We examine six initialization strategies, including those based on coupled-cluster singles and doubles (CCSD), Møller-Plesset second-order perturbation theory (MP2), data-driven coupled-cluster (DDCC), and trivial (zeroes and random) initializations, across twelve molecular systems and three basis sets (STO-3G, cc-pVDZ, and aug-cc-pVDZ). We find that while the mean absolute percentage errors (MAPEs) between the alternative and CCSD-initialized t2-amplitudes span many orders of magnitude, the resulting SQD energies are largely insensitive to this variation. In particular, most initializations recover energies within chemical accuracy (+/-1.6 mEh) of the CCSD reference, with convergence improving as the basis set size increases. Notably, random initialization achieves performance competitive with CCSD across all basis sets, while zeroes initialization, despite having smaller deviations from CCSD, yields the worst energy agreement. Our results highlight that the proximity to the CCSD initialization is not a reliable predictor of the quality of electronic energies. These findings establish that configuration recovery within SQD, rather than circuit initialization, is the dominant factor governing energy accuracy, and suggest that computationally cheaper initialization strategies are viable alternatives to CCSD for QCSC workflows
The unitary cluster Jastrow (UCJ) ansatz and its variant known as local UCJ (LUCJ) are promising choices for variational quantum algorithms for chemistry due to their combination of physical motivation and hardware efficiency. The parameters of these ansatzes can be initialized from the output of a coupled cluster, singles and doubles (CCSD) calculation performed on a classical computer. However, truncating the number of repetitions of the ansatz, as well as discarding interactions to accommodate the connectivity constraints of near-term quantum processors, degrade the approximation to CCSD and the resulting energy accuracy. In this work, we propose two methods to improve the parameter initialization. The first method, which is applicable to both expectation value- and sample-based algorithms, uses compressed double factorization of the CCSD amplitudes to improve or recover the CCSD approximation. The second method, which is applicable to sample-based algorithms, uses approximate tensor network simulation to improve the quality of samples produced by the ansatz circuit. We validate our methods using exact state vector simulation on systems of up to 52 qubits, as well as experiments on superconducting quantum processors using up to 65 qubits. Our results indicate that our methods can significantly improve the output of both expectation value- and sample-based quantum algorithms.
We present a large-scale experimental study of quantum-computing-based molecular simulation carried out on IQM's Sirius 24-qubit superconducting processor, utilizing up to 16 operational qubits. The work employs Sample-based Quantum Diagonalization (SQD) together with the Local Unitary Cluster Jastrow (LUCJ) ansatz to estimate ground-state energies for a set of benchmark molecules, including H2, LiH, BeH2, H2O, and NH3. In addition, we introduce a Linear-CNOT variant of the Unitary Coupled-Cluster Singles and Doubles (LCNot-UCCSD) ansatz within the SQD workflow, trading higher circuit depth for reduced classical preprocessing. A comparison between these ansätze is provided, clarifying their respective strengths, limitations, and suitability for near-term quantum hardware. We further explore potential energy landscapes through 1D scans for H2 and HeH+ using both STO-3G and 6-31G basis sets, and for LiH and BeH2 in STO-3G. Extending beyond this, we demonstrate the experimental construction of a full 2D potential energy surface for the water molecule on quantum hardware, mapped over a 32 × 32 grid in bond length and bond angle. To move beyond small benchmark systems, we combine SQD(LUCJ) with Density Matrix Embedding Theory (DMET) to compute active-space energies for a set of ligand-like molecules, as well as the pharmacologically relevant amantadine system. Across all studies, the majority of quantum-computed energies agree with reference FCI results, as well as with DMET-CASCI energies for embedded systems, to within chemical accuracy for the chosen basis sets. These results demonstrate the reliability of sample-based diagonalization approaches and underscore the potential of hybrid embedding strategies for extending quantum simulations to increasingly complex molecular systems, while also highlighting their practicality on current IQM quantum hardware.
Sample-based Quantum Diagonalization (SQD) is a hybrid quantum-classical method that replaces variational optimization with a self-consistent recovery loop over QPU samples. Although SQD is considered robust to noisy samples and imperfect classical inputs, its robustness across practical deployment choices has not been systematically analyzed. As a result, shot budgets, qubit layouts, noise mitigation strategies, and the coupled-cluster singles and doubles (CCSD) amplitudes that initialize the ansatz are often chosen without clear empirical guidance. We analyze SQD robustness on IBM Heron hardware across these dimensions. Structured CCSD-amplitude perturbations, including complete zeroing, produce only modest energy shifts from the clean baseline. Differences across layouts and noise-mitigation settings are large in the first recovery iteration but narrow within a few iterations. Accuracy saturates at moderate shot budgets, while very large budgets slightly worsen recovered energies, likely because working-set selection limits the value of additional samples. These results identify where SQD provides genuine deployment robustness and where its limits remain.
In the context of quantum computing, efficient resource management is crucial for optimizing throughput on cloud-based platforms and maximizing hardware utilization. In the present work, we propose an approach to tackle quantum chemistry problems via quantum multi-programming of the Local Unitary Cluster Jastrow (LUCJ) ansätze. The ground-state energy of the molecular system is obtained via Sample-based quantum diagonalization (SQD), further refined by its extended version (ext-SQD). Building upon the Qiskit Experiments package, which already supports parallel execution functionality for general tasks, we developed a novel parallel experiment class tailored for quantum chemistry problems. Cross-talk is a known issue in the multi-programming frameworks and can corrupt the ground-energy estimation of the simulated systems. To assess its impact within our approach, we simulated two conformations of the ethanol molecule: one at the equilibrium state (EtOHEq), and one with the O-H bond stretched to 1.2 A˚ (EtOH1.2). We defined three different layouts that we executed in a randomized fashion, alternating serial and parallel execution within 10 independent replicates. The single modality of each circuit was kept as a baseline to evaluate the effect of cross-talk induced by quantum multi-programming. The energies obtained at the first-, last- and ext-SQD iteration were compared to the classical Heat-bath Configuration Interaction (HCI) reference. Our findings highlight the viability of a quantum multi-programming workflow for quantum chemistry as the robust post-processing protocol effectively mitigates possible cross-talk induced noise. At the final step of the configuration recovery process, the energy difference relative to the HCI reference is negligible, within 0.001 kcal/mol.
Ground-State Energy Estimation of HeH+, ArH+, and H2O via Sample-Based Quantum Diagonalization
Accurate ground-state energies are essential for understanding molecular structure, chemical bonding, and reaction energetics in quantum chemistry. In this work, we investigate the ground-state properties of the molecular systems HeH+, ArH+, and H2O using Sample-Based Quantum Diagonalization (SQD), a hybrid quantum-classical framework designed for near-term quantum devices. Unlike variational approaches such as VQE, which require deep parameterized circuits and repeated expectation-value measurements, SQD reconstructs a low-energy determinant subspace directly from measured bitstrings. For the present calculations, bitstrings were generated on IBM quantum hardware using shallow local unitary cluster Jastrow (LUCJ) circuits whose parameters were constructed from the t1 and t2 amplitudes of coupled-cluster singles and doubles (CCSD) calculations based on restricted Hartree--Fock (RHF) references. From these samples, we compute ground-state potential-energy curves of HeH+, ArH+, and H2O with the 6-31G and cc-pVDZ basis sets. For all three systems, the SQD results obtained with the cc-pVDZ basis closely follow the corresponding same-basis CCSD energies and reproduce the equilibrium-region trends of the potential-energy curves. HeH+ and ArH+ were chosen as simple yet astrophysically important molecular-ion benchmarks, while H2O was included as a representative polyatomic molecule to assess the applicability of SQD beyond diatomic ionic systems. At the adopted equilibrium geometries, the deviations from the same-active-space CASCI references are 0.00, 2.51, and 6.34 mHa for HeH+, ArH+, and H2O, respectively. These results demonstrate the feasibility of hardware-assisted SQD for the present benchmark systems and motivate further studies of its accuracy and computational scaling for larger molecular active spaces.
The Selected Quantum Doubles (SQD) methods are among the most reliable approaches for quantum computation, capable of achieving high-accuracy simulations of electronic structure problems. Despite their strengths, SQD methods encounter challenges related to the selection of the initial state and the efficient management of extensive configuration spaces. This is particularly due to the presence of numerous configurations with low significance, which can limit scalability and accuracy. To address these issues, we have developed a perturbative quantum method capable of generating an initial state that is both accurate and flexible, alongside a procedure to manage the scalability of the method. Regarding the first objective, a parameterized Unitary Coupled Cluster Doubles (UCCD) approach has been developed, which generates a wavefunction comparable in quality to the Coupled Cluster Doubles (CCD) reference state. At this juncture, it is possible to augment this parameterized UCCD state to incorporate the principal single excited configurations. This augmentation step is essential to ensure that the initial state possesses sufficient flexibility to account for configurations that are combinations of single and double excited configurations. The second objective is the enhancement of the methodology's scalability. This objective is achieved by first identifying, through a perturbative approach, the most significant higher-order configurations. This allows for a smaller configurational CI Hamiltonian. Conversely, the second set of configurations will not be included in the Hamiltonian CI but will be evaluated solely within a perturbative framework using second-order perturbation theory (PT2). This combined approach leverages the strengths of both variational and perturbative methods, enabling the simulation to closely approximate Full Configuration Interaction (FCI) results while operating within a significantly reduced configurational space. This methodology resembles the most common Selected Configurations Interaction plus Perturbation methodology, while distinguishing itself through an improved selection process, which will be further refined in the future. The method will be tested on a highly correlated molecular system (linear chain of 8 Hydrogen) in minimal basis set. The molecule has been optimized in pyscf with MP2 method and def2-svp basis set.