Full Citation: E. R. Davidson, "The Right Answer for the Right Reason: My Personal Goal for Quantum Chemistry", Annu. Rev. Phys. Chem. 70, in press (2019). DOI: 10.1146/annurev-physchem-042018-052300.

Discussed on January 30, 2019.

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Description

This review article stresses the importance of getting "the right answer for the right reason" in theoretical chemistry. Davidson points out flaws in semi-empirical reasoning and the black-box approach and provides solutions to these problems. The author gives a synopsis of several of his research projects.

The prevalence of error is acceptable given that they are accounted for in systematic fashion. The level of theory must be assessed for its robustness and computational efficiency. As such, choosing a proper Hamiltonian and basis set is pertinent to obtaining the correct physics--and thus the correct energetics, spectral properties, geometries, etc. Davidson narrates his experiences with different chemical problems pertaining to topics such as: bond dissociation, intramolecular charge distribution, excited-state calculations, electronic correlation, spin, bonding, fluorescence spectroscopy, and photoelectron spectroscopy.

Inline Comedic Feature: Michael Dewar had petitioned to the NSF to stop funding ab initio methods research on the grounds of fiscal strain.

Keywords

Size consistency; Configuration interaction; Davidson eigenvalue method; Dyson orbitals; Iterative natural orbitals; McMurchie-Davidson recurrence relations; Spin