Time-Dependent Coupled-Cluster Theory of Multireference Systems

TL;DR

This paper introduces a time-dependent coupled-cluster method for multireference systems that accurately propagates quantum states and computes properties, demonstrated on a Hubbard-like model.

Contribution

The work develops a novel time-dependent coupled-cluster formalism for multireference systems, including equations of motion and application to a model Hamiltonian.

Findings

Reproduces exact results for observables, populations, and coherences.

Provides a size-extensive method for multireference electronic systems.

Derives asymmetric matrix elements and resymmetrization for quantum consistency.

Abstract

In this work we present a coupled-cluster theory for the propagation of multireference electronic systems initiating at general quantum mechanical states. Our formalism is based on the infinitesimal analysis of modified cluster operators, from which we extract a set of additional operators and their equations of motion. These cluster operators then can be used to compute electronic properties of interest in a size extensive manner. The equations derived herein are also studied for the free propagation of linear superpositions. In this regime, we derive asymmetric matrix elements for observables, and a resymmetrization factor so they become consistent with their quantum mechanical counterparts. Our formalism is applied to a four-electron/four-level model with a Hubbard-like Hamiltonian, where we show that it reproduces the numerically exact results for observables, populations, and coherences.