Quantitative quantum chemistry

Trygve Helgaker*, Wim Klopper, David P. Tew

*Corresponding author for this work

Research output: Contribution to journalReview article (Academic Journal)peer-review

171 Citations (Scopus)

Abstract

We review the current status of quantum chemistry as a predictive tool of chemistry and molecular physics, capable of providing highly accurate, quantitative data about molecular systems. We begin by reviewing wave-function based electronic-structure theory, emphasizing the N-electron hierarchy of coupled-cluster theory and the one-electron hierarchy of correlation-consistent basis sets. Following a discussion of the slow basis-set convergence of dynamical correlation and basis-set extrapolations, we consider the methods of explicit correlation, from the early work of Hylleraas in the 1920s to the latest developments in such methods, capable of yielding high-accuracy results in medium-sized basis sets. Next, we consider the small corrections to the electronic energy (high-order virtual excitations, vibrational, relativistic, and diagonal Born-Oppenheimer corrections) needed for high accuracy and conclude with a review of the composite methods and computational protocols of electronic-structure theory.

Original languageEnglish
Article number905331311
Pages (from-to)2107-2143
Number of pages37
JournalMolecular Physics
Volume106
Issue number16-18
DOIs
Publication statusPublished - 2008

Keywords

  • electronic-structure theory
  • basis-set extrapolation
  • explicit correlation
  • coupled-cluster theory
  • COUPLED-CLUSTER THEORY
  • COMPLETE BASIS-SET
  • CORRELATED GAUSSIAN FUNCTIONS
  • MOLECULAR CORRELATION ENERGIES
  • DIRECT PERTURBATION-THEORY
  • AB-INITIO THERMOCHEMISTRY
  • 2ND-ORDER CORRELATION ENERGIES
  • CONSISTENT COMPOSITE APPROACH
  • DENSITY-FUNCTIONAL THEORY
  • QUADRATIC CONFIGURATION-INTERACTION

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