Ground-State Energy Estimation of HeH${}^{+}$, ArH${}^{+}$, and H${}_2$O via Sample-Based Quantum Diagonalization

Abstract

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 H${}_2$O 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 $t_1$ and $t_2$ 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 H${}_2$O 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 H${}_2$O 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 H${}_2$O, 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.

Comments: 19 pages, 2 figures, 2 tables