Spin-state energetics of heme-related models with the variational quantum eigensolver (2504.08494v1)

Abstract: We present numerical calculations of the energetic separation between different spin states (singlet, triplet and quintet) for a simplified model of a deoxy-myoglobin protein using the variational quantum eigensolver (VQE) algorithm. The goal is to gain insight into the workflow and challenges of VQE simulations for transition metal complexes, with emphasis on methodology over hardware-specific implementation. The numerical calculations are performed using an in-house statevector simulator with single- and multi-reference trial wavefunctions based on the k-unitary pair coupled-cluster generalized singles and doubles or k-UpCCGSD ansatz. The spin-state energetics for active spaces of increasing size up to 10 spatial orbitals (20 spin orbitals or qubits) are computed with VQE and were found to agree with the classical complete active self-consistent field or CASSCF method to within 1-4 kcal/mol. We evaluate relevant multi-reference diagnostics and show that the spin states computed with VQE possess a sufficient degree of multi-reference character to highlight the presence of strong electron correlation effects. Our numerical simulations show that in the ideal case, the VQE algorithm is capable of reproducing spin-state energetics of strongly correlated systems such as transition metal complexes for both single- and multi-reference trial wavefunctions, asymptotically achieving good agreement with results from classical methods as the number of active orbitals increases.