Embedded equation-of-motion coupled-cluster theory for electronic excitation, ionisation, electron attachment, and electronic resonances

Abstract

The projection-based quantum embedding method is applied to a comprehensive set of electronic states. We embed different variants of equation-of-motion coupledcluster singles and doubles (EOM-CCSD) theory in density functional theory and investigate electronically excited states of valence, Rydberg, and charge-transfer character, valenceand core-ionized states, as well as bound and temporary radical anions. The latter states, which are unstable towards electron loss, are treated by means of a complex-absorbing potential. Besides transition energies, we also present Dyson orbitals and natural transition orbitals for embedded EOM-CCSD. We benchmark the performance of the embedded EOM-CCSD methods against full EOM-CCSD using small organic molecules microsolvated by a varying number of water molecules as test cases. Our results illustrate that embedded EOM-CCSD describes ionization and valence excitation very well and that these transitions are quite insensitive towards technical details of the embedding procedure. On the contrary, more care is required when dealing with Rydberg excitations or electron attachment. For the latter type of transition in particular, the use of long-range corrected density functionals is mandatory and truncation of the virtual orbital space –which is indispensable for the application of projection-based embedding to large systems– proves to be difficult.