Quantum Information-Assisted Complete Active Space Optimization (QICAS)

TL;DR

QICAS introduces a quantum information-based method for optimizing active spaces in multiconfigurational calculations, improving accuracy and convergence for complex molecules by assessing electronic correlation unambiguously.

Contribution

It presents a novel quantum information-assisted scheme that enhances active space selection and orbital optimization in multiconfigurational methods, especially for challenging systems.

Findings

QICAS achieves chemical accuracy in small molecules.

Reduces iterations needed for CASSCF convergence in complex systems.

Validates that minimal entanglement correlates with optimal active spaces.

Abstract

Automated active space selection is arguably one of the most challenging and essential aspects of multiconfigurational methods. In this work we propose an effective quantum information-assisted complete active space optimization (QICAS) scheme. What sets QICAS apart from other correlation-based selection schemes is (i) the use of unique measures from quantum information that assess the correlation in electronic structures in an unambiguous and predictive manner, and (ii) an orbital optimization step that minimizes the correlation discarded by the active space approximation. Equipped with these features QICAS yields for smaller correlated molecules sets of optimized orbitals with respect to which the CASCI energy reaches the corresponding CASSCF energy within chemical accuracy. For more challenging systems such as the Chromium dimer, QICAS offers an excellent starting point for CASSCF by greatly reducing the number of iterations required for numerical convergence. Accordingly, our study validates a profound empirical conjecture: the energetically optimal non-active spaces are predominantly those that contain the least entanglement.