Second-Order Active-Space Embedding Theory.

Quantum embedding schemes are a promising way to extend multireference computations to large molecules with strong correlation effects localized on a small number of atoms. This work introduces a second-order active-space embedding theory [ASET(2)] which improves upon mean-field frozen embedding by treating fragment-environment interactions via an approximate canonical transformation. The canonical transformation employed in ASET(2) is formulated using the driven similarity renormalization group. The ASET(2) scheme is benchmarked on the N═N bond dissociation in pentyldiazene, the S 0 to S 1 excitation in 1-octene, and the interaction energy of the O 2 -benzene complex. The ASET(2) explicit treatment of fragment-environment interactions beyond the mean-field level generally improves the accuracy of embedded computations, and it becomes necessary to achieve an accurate description of excitation energies of 1-octene and the singlet-triplet gap of the O 2 -benzene complex.