ONETEP + TOSCAM: uniting dynamical mean field theory and linear-scaling density functional theory

TL;DR

This paper presents a unified computational approach combining dynamical mean field theory with linear-scaling density functional theory, enabling the study of strongly correlated systems within complex environments.

Contribution

It introduces a novel integration of DMFT and DFT within ONETEP and TOSCAM, allowing for accurate simulations of complex, strongly correlated materials with environmental effects.

Findings

Successfully applied to iron porphyrin, revealing quantum behavior of iron 3d electrons during photodissociation.

Demonstrated the method's capability to handle complex systems with transition metals and lanthanides.

Extended formalism to non-orthogonal basis sets used in ONETEP.

Abstract

We introduce the unification of dynamical mean field theory (DMFT) and linear-scaling density functional theory (DFT), as recently implemented in ONETEP, a linear-scaling DFT package, and TOSCAM, a DMFT toolbox. This code can account for strongly correlated electronic behavior while simultaneously including the effects of the environment, making it ideally suited for studying complex and heterogeneous systems containing transition metals and lanthanides, such as metalloproteins. We systematically introduce the necessary formalism, which must account for the non-orthogonal basis set used by ONETEP. In order to demonstrate the capabilities of this code, we apply it to carbon monoxide-ligated iron porphyrin and explore the distinctly quantum-mechanical character of the iron $3d$ electrons during the process of photodissociation.