We explore the performance of a recently-introduced N5-scaling
excited-state-specific second order perturbation theory (ESMP2) on the singlet
excitations of the Thiel benchmarking set. We find that, without
regularization, ESMP2 is quite sensitive to π system size, performing well
in molecules with small π systems but poorly in those with larger π
systems. With regularization, ESMP2 is far less sensitive to π system size
and shows a higher overall accuracy on the Thiel set than CC2, EOM-CCSD, CC3,
and a wide variety of time-dependent density functional approaches.
Unsurprisingly, even regularized ESMP2 is less accurate than multi-reference
perturbation theory on this test set, which can in part be explained by the
set's inclusion of some doubly excited states but none of the strong charge
transfer states that often pose challenges for state-averaging. Beyond
energetics, we find that the ESMP2 doubles norm offers a relatively low-cost
way to test for doubly excited character without the need to define an active
space
