Extension of the Active-Orbital-Based and Adaptive CC($P$;$Q$) Approaches to Excited Electronic States: Application to Potential Cuts of Water

Abstract

We report the first study using active-orbital-based and adaptive CC($P$;$Q$) approaches to describe excited electronic states. These CC($P$;$Q$) methodologies are applied, alongside their completely renormalized (CR) coupled-cluster (CC) and equation-of-motion (EOM) CC counterparts, to recover the ground- and excited-state potential cuts of the water molecule along the O-H bond-breaking coordinate obtained in the parent CC/EOMCC calculations with a full treatment of singles, doubles, and triples (CCSDT/EOMCCSDT). We demonstrate that the active-orbital-based and adaptive CC($P$;$Q$) approaches closely approximate the CCSDT/EOMCCSDT data using significantly reduced computational costs while improving the CR-CC and CR-EOMCC energetics in stretched regions of the O-H bond-breaking potentials.

13 pages, 3 tables, and 1 figure. Supporting Data as an ancillary file. This article has been accepted for publication in Chemical Physics Letters. After it is published, it will be found at