Striking the Right Balance of Encoding Electron Correlation in the Hamiltonian and the Wavefunction Ansatz

TL;DR

This paper discusses methods to improve multi-configurational electronic structure calculations by balancing static and dynamic electron correlation, supported by tensor network data and proposing simplified correlator models.

Contribution

It reviews recent explicit correlation approaches for multi-configurational methods and advocates for structure-independent correlator expressions to enhance universality.

Findings

Tensor network data supports the proposed approaches.

Explicit correlation methods face key obstacles.

Simple electrons-only correlator expressions are promising.

Abstract

Multi-configurational electronic structure theory delivers the most versatile approximations to many-electron wavefunctions, flexible enough to deal with all sorts of transformations, ranging from electronic excitations, to open-shell molecules and chemical reactions. Multi-configurational models are therefore essential to establish universally applicable, predictive ab initio methods for chemistry. Here, we present a discussion of explicit correlation approaches which address the nagging problem of dealing with static and dynamic electron correlation in multi-configurational active-space approaches. We review the latest developments and then point to their key obstacles. Our discussion is supported by new data obtained with tensor network methods. We argue in favor of simple electrons-only correlator expressions that may allow one to define transcorrelated models in which the correlator does not bear a dependence on molecular structure.