Correlation-Driven Phenomena in Periodic Molecular Systems from Variational Two-electron Reduced Density Matrix Theory

TL;DR

This paper extends variational two-electron reduced density matrix theory to accurately predict strong correlation effects in periodic molecular systems, successfully capturing phenomena like the Mott transition and polyradical formation.

Contribution

It generalizes 2-RDM theory for periodic systems, enabling direct computation of energies and properties in strongly correlated materials with larger active spaces.

Findings

Predicts Mott metal-insulator transition in hydrogen chains

Captures length-dependent polyradical formation in acenes

Shows significant energy and correlation changes with periodic boundary conditions

Abstract

Correlation-driven phenomena in molecular periodic systems are challenging to predict computationally not only because such systems are periodically infinite but also because they are typically strongly correlated. Here we generalize the variational two-electron reduced density matrix (2-RDM) theory to compute the energies and properties of strongly correlated periodic systems. The 2-RDM of the unit cell is directly computed subject to necessary $N$-representability conditions such that the unit-cell 2-RDM represents at least one $N$-electron density matrix. Two canonical but non-trivial systems, periodic metallic hydrogen chains and periodic acenes, are treated to demonstrate the methodology. We show that, while single-reference correlation theories do not capture the strong (static) correlation effects in either of these molecular systems, the periodic variational 2-RDM theory predicts the Mott metal-to-insulator transition in the hydrogen chains and the length-dependent polyradical formation in acenes. For both hydrogen chains and acenes the periodic calculations are compared with previous non-periodic calculations with the results showing a significant change in energies and increase in the electron correlation from the periodic boundary conditions. The 2-RDM theory, which allows for much larger active spaces than are traditionally possible, is applicable to studying correlation-driven phenomena in general periodic molecular solids and materials.