Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes

TL;DR

This paper advances density functional theory embedding techniques by developing spin-dependent potentials and an orbital-occupation-freezing method, enabling more accurate and stable correlated wavefunction calculations for open-shell systems and transition metal complexes.

Contribution

The authors introduce new methods for WFT-in-DFT embedding, including spin-dependent potentials and an orbital-occupation-freezing technique, improving accuracy and convergence for open-shell and transition metal systems.

Findings

WFT-in-DFT reproduces CCSD(T) energies within 0.1 kcal/mol for ethylene-propylene dimer.

Eliminates errors in dispersion interactions from conventional XC functionals.

Restricted open-shell embedding outperforms unrestricted due to reduced spin contamination.

Abstract

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the accuracy and stability of WFT-in-DFT embedding calculations. In particular, we develop spin-dependent embedding potentials in both restricted and unrestricted orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and we develop an orbital-occupation-freezing technique to improve the convergence of optimized effective potential (OEP) calculations that arise in the evaluation of the embedding potential. The new techniques are demonstrated in applications to the van-der-Waals-bound ethylene-propylene dimer and to the hexaaquairon(II) transition-metal cation. Calculation of the dissociation curve for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating errors in the dispersion interactions due to conventional exchange-correlation (XC) functionals while simultaneously avoiding errors due to subsystem partitioning across covalent bonds. Application of WFT-in-DFT embedding to the calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II) cation reveals that the majority of the dependence on the DFT XC functional can be eliminated by treating only the single transition-metal atom at the WFT level; furthermore, these calculations demonstrate the substantial effects of open-shell contributions to the embedding potential, and they suggest that restricted open-shell WFT-in-DFT embedding provides better accuracy than unrestricted open-shell WFT-in-DFT embedding due to the removal of spin contamination.