Green's function coupled cluster formulations utilizing extended inner excitations

TL;DR

This paper introduces an extended Green's function coupled cluster (GFCC) method with higher excitation levels for inner auxiliary operators, improving spectral predictions and pole locations in quantum chemistry calculations.

Contribution

The paper proposes a new GFCC-i(n,m) approximation with an 'n+1' rule for size-extensivity, and demonstrates the GFCC-i(2,3) method's improved spectral accuracy over GFCCSD.

Findings

GFCC-i(2,3) yields better spectral agreement with experiments.

Enhanced resolution of satellite peaks in spectral functions.

More accurate peak positions compared to GFCCSD.

Abstract

In this paper we analyze new approximations of the Green's function coupled cluster (GFCC) method where locations of poles are improved by extending the excitation level of inner auxiliary operators. These new GFCC approximations can be categorized as GFCC-i($n,m$) method, where the excitation level of the inner auxiliary operators ($m$) used to describe the ionization potentials and electron affinities effects in the $N$$-$1 and $N$+1 particle spaces is higher than the excitation level ($n$) used to correlate the ground-state coupled cluster wave function for the $N$-electron system. Furthermore, we reveal the so-called "$n$+1" rule in this category (or the GFCC-i($n$,$n$+1) method), which states that in order to maintain size-extensivity of the Green's function matrix elements, the excitation level of inner auxiliary operators $X_p(\omega)$ and $Y_q(\omega)$ cannot exceed $n$+1. We also discuss the role of the moments of coupled cluster equations that in a natural way assures these properties. Our implementation in the present study is focused on the first approximation in this GFCC category, i.e. the GFCC-i(2,3) method. As our first practice, we use the GFCC-i(2,3) method to compute the spectral functions for the N$_2$ and CO molecules in the inner and outer valence regimes. In comparison with the GFCCSD results, the computed spectral functions from the GFCC-i(2,3) method exhibit better agreement with the experimental results and other theoretical results, particularly in terms of providing higher resolution of satellite peaks and more accurate relative positions of these satellite peaks with respect to the main peak positions.