Stochastic resolution of identity to CC2 for large systems: Excited-state gradients and derivative couplings

Abstract

Excited-state gradients and derivative couplings are critical for simulating excited-state dynamics. However, their calculations are very expensive within the coupled-cluster framework due to the steep scaling. In this work, we present two implementations of stochastic resolution of identity to CC2 (sRI-CC2) for excited-state analytical gradients and derivative couplings. The first method employs sRI for both Coulomb and exchange terms, reducing the formal scaling to cubic. However, this method has a significant stochastic noise. Consequently, we introduce a substitute, termed partial sRI-CC2, which applies sRI selectively to the exchange terms only. The partial sRI-CC2 shows a quartic scaling with a modest prefactor, rendering it a practical alternative. Compared to conventional RI-CC2, the partial sRI-CC2 can handle systems with hundreds or even thousands of electrons. This work is an extension to our previous implementation of sRI-CC2 method and provides essential ingredients for large-scale nonadiabatic dynamics.