## 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 language | English |
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Article number | 905331311 |

Pages (from-to) | 2107-2143 |

Number of pages | 37 |

Journal | Molecular Physics |

Volume | 106 |

Issue number | 16-18 |

DOIs | |

Publication status | Published - 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