Projection-Based Wavefunction-in-DFT Embedding

Abstract

Complex chemical systems present challenges to electronic structure theory stemming from large system sizes, subtle interactions, coupled dynamical time scales, and electronically nonadiabatic effects. New methods are needed to perform reliable, rigorous, and affordable electronic structure calculations for simulating the properties and dynamics of such systems. This Account reviews projection-based quantum embedding for electronic structure, which provides a formally exact method for density functional theory (DFT) embedding. The method also provides a rigorous and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction (WF) method while the remainder of the system is described at the level of DFT. A key advantage of projection-based embedding is that it can be formulated in terms of an extremely simple level-shift projection operator, which eliminates the need for any optimized effective potential calculation or kinetic energy functional approximation while simultaneously ensuring that no extra programming is needed to perform WF-in-DFT embedding with an arbitrary WF method. The current work presents the theoretical underpinnings of projection-based embedding, describes use of the method for combining wavefunction and density functional theories, and discusses technical refinements that have improved the applicability and robustness of the method. Applications of projection-based WF-in-DFT embedding are also reviewed, with particular focus on recent work on transition-metal catalysis, enzyme reactivity, and battery electrolyte decomposition. In particular, we review the application of projection-based embedding for the prediction of electrochemical potentials and reaction pathways in a Co-centered hydrogen evolution catalyst. Projection-based WF-in-DFT calculations are shown to provide quantitative accuracy while greatly reducing the computational cost compared with a reference coupled cluster calculation on the full system. Additionally, projection-based WF-in-DFT embedding is used to study the mechanism of citrate synthase; it is shown that projection-based WF-in-DFT largely eliminates the sensitivity of the potential energy landscape to the employed DFT exchange–correlation functional. Finally, we demonstrate the use of projection-based WF-in-DFT to study electron transfer reactions associated with battery electrolyte decomposition. Projection-based WF-in-DFT embedding is used to calculate the oxidation potentials of neat ethylene carbonate (EC), neat dimethyl carbonate (DMC), and 1:1 mixtures of EC and DMC in order to overcome qualitative inaccuracies in the electron densities and ionization energies obtained from conventional DFT methods. By further embedding the WF-in-DFT description in a molecular mechanics point-charge environment, this work enables an explicit description of the solvent and ensemble averaging of the solvent configurations. Looking forward, we anticipate continued refinement of the projection-based embedding methodology as well as its increasingly widespread application in diverse areas of chemistry, biology, and materials science.

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