Exploring Ground and Excited States via Single Reference Coupled-Cluster Theory and Algebraic Geometry

TL;DR

This paper investigates the root structure of coupled cluster equations in quantum chemistry using algebraic geometry, demonstrating that multiple CC roots can accurately approximate excited states and dissociation processes in small molecules.

Contribution

It applies algebraic geometry techniques to analyze coupled cluster equations and assesses their effectiveness in approximating excited states and dissociation energies.

Findings

Multiple CC roots accurately describe excited state energies.

CC methods provide high-accuracy approximations to dissociation processes.

Algebraic geometry techniques effectively analyze root structures.

Abstract

The exploration of the root structure of coupled cluster equations holds both foundational and practical significance for computational quantum chemistry. This study provides insight into the intricate root structures of these non-linear equations at both the CCD and CCSD level of theory. We utilize computational techniques from algebraic geometry, specifically the monodromy and parametric homotopy continuation methods, to calculate the full solution set. We compare the computed CC roots against various established theoretical upper bounds, shedding light on the accuracy and efficiency of these bounds. We hereby focus on the dissociation processes of four-electron systems such as (H$_2$)$_2$ in both D$_{2{\rm h}}$ and D$_{\infty {\rm h}}$ configurations, H$_4$ symmetrically distorted on a circle, and lithium hydride. We moreover investigate the ability of single-reference coupled cluster solutions to approximate excited state energies. We find that multiple CC roots describe energies of excited states with high accuracy. Our investigations reveal that for systems like lithium hydride, CC not only provides high-accuracy approximations to several excited state energies but also to the states themselves.