文档介绍：REVIEWS OF MODERN PHYSICS, VOLUME 79, JANUARY–MARCH 2007
Coupled-cluster theory in quantum chemistry
Rodney J. Bartlett and Monika Musiał*
Quantum Theory Project, Departments of Chemistry and Physics, University of Florida,
Gainesville, Florida 32611-8435, USA
͑Published 22 February 2007͒
Today, coupled-cluster theory offers the most accurate results among the practical ab initio
electronic-structure theories applicable to moderate-sized molecules. Though it was originally
proposed for problems in physics, it has seen its greatest development in chemistry, enabling an
extensive range of applications to molecular structure, excited states, properties, and all kinds of
spectroscopy. In this review, the essential aspects of the theory are explained and illustrated with
informative numerical results.
DOI: .291 PACS number͑s͒: , , ,
CONTENTS chemistry circles, we begin with a quote from Ken Wil-
son ͑1989͒:
I. Perspective on the Molecular Electronic Problem 291 “Ab initio quantum chemistry is an -
II. Plan for Review 293 putational area that is fifty years ahead of lattice
…
III. Some Essential Preliminaries 294 gauge theory and a rich source of new ideas and
A. Configuration interaction 295 new approaches to putation of many fer-
B. Perturbation theory 296 mion systems.”
C. Coupled-cluster theory 297 Driving these developments are the types of problems
IV. Normal-Ordered Hamiltonian 299 addressed by quantum chemists, as shown in Fig. 1. Pri-
͑͒
V. Coupled-Cluster Equations 302 mary among these are potential-energy surfaces PES
A. Double excitations theory 304 which describe the behavior of the electronic energy
B. Choice of single determinant reference function 305 with respect to the locations of the nuclei, subject to the
C. Single excitations theory 307 underlying Born-Oppenheimer or clamped nuclei ap-
D. Triple and quadruple excitations theory 308 proximation