Measuring Electron Correlation. The Impact of Symmetry and Orbital Transformations

Abstract

In this perspective, the various measures of electron correlation used in wavefunction theory, density functional theory and quantum information theory are briefly reviewed. We then focus on a more traditional metric based on dominant weights in the full configuration solution and discuss its behaviour with respect to the choice of the $N$-electron and the one-electron basis. The impact of symmetry is discussed and we emphasize that the distinction between determinants, configuration state functions and configurations as reference functions is useful because the latter incorporate spin-coupling into the reference and should thus reduce the complexity of the wavefunction expansion. The corresponding notions of single determinant, single spin-coupling and single configuration wavefunctions are discussed and the effect of orbital rotations on the multireference character is reviewed by analysing a simple model system. In molecular systems, the extent of correlation effects should be limited by finite system size and in most cases the appropriate choices of one-electron and $N$-electron bases should be able to incorporate these into a low-complexity reference function, often a single configurational one.

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• Quantum Simulations of Chemistry in First Quantization with any Basis Set
• Spin coupling is all you need: Encoding strong electron correlation in molecules on quantum computers
• Resonating holes vs molecular spin-orbit coupled states in group-5 lacunar spinels
• Quantum Computation of Electronic Structure with Projector Augmented-Wave Method and Plane Wave Basis Set
• Orbital-Free Quasi-Density Functional Theory
• The Electronic Structure of the Hydrogen Molecule: A Tutorial Exercise in Classical and Quantum Computation