Quantum-Centric Computational Study of Methylene Singlet and Triplet States.

This study involves quantum simulations of the dissociation of the ground-state triplet and first excited singlet states of the CH(2) molecule (methylene), which are relevant for interstellar and combustion chemistry. These were modeled as (6e, 23o) systems using 52 qubits on a quantum processor by applying the sample-based quantum diagonalization (SQD) method within a quantum-centric supercomputing framework. We evaluated the ability of SQD to provide accurate results of the singlet-triplet gap in comparison to selected configuration interaction (SCI) calculations and experimental values. To our knowledge, this is the first study of an open-shell system (the CH(2) triplet) using SQD. To obtain accurate energy values, we implemented post-SQD orbital optimization and employed a warm-start approach using previously converged states. The results for the singlet state dissociation were highly accurate, differing by only a few milli-Hartrees from the SCI reference values. Similarly, the SQD-calculated singlet-triplet energy gap aligned well with both experimental and SCI values, underscoring the method's capability to capture key features of CH(2) chemistry. However, the triplet state exhibited greater variability, likely due to differences in bit-string handling within the SQD method for open- versus closed-shell systems and the inherently complex wavefunction character of the triplet state. These findings highlight the strengths and limitations of SQD for modeling open-shell systems while laying a foundation for its application in large-scale electronic structure studies using quantum algorithms.