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.Comment: 11 pages, 5 figures, 2 table
