Real-Time Coupled-Cluster Approach for the Cumulant Green's Function

J Chem Theory Comput. 2020 Nov 10;16(11):6983-6992. doi: 10.1021/acs.jctc.0c00639. Epub 2020 Oct 28.

Abstract

Green's function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Here, we develop the cumulant form of the one-electron Green's function using a real-time coupled-cluster equation-of-motion approach, in an extension of our previous study (Rehr J.; et al. J. Chem. Phys. 2020, 152, 174113). The approach yields a nonperturbative expression for the cumulant in terms of the solution to a set of coupled first-order, nonlinear differential equations. The method thereby adds nonlinear corrections to traditional cumulant methods, which are linear in the self-energy. The approach is applied to the core-hole Green's function and is illustrated for a number of small molecular systems. For these systems, we find that the nonlinear contributions yield significant improvements, both for quasiparticle properties such as core-level binding energies and for inelastic losses that correspond to satellites observed in photoemission spectra.