Benchmarking state-of-the-art ab initio thermochemical predictions with accurate pulsed-field ionization photoion - photoelectron measurements

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Original languageEnglish
Pages (from-to)823-829
Journal / PublicationAccounts of Chemical Research
Issue number11
Publication statusPublished - Nov 2006
Externally publishedYes


This Account presents a comparison between highly precise thermochemical data, including ionization energies, 0 K dissociative photoionization thresholds, and 0 K bond dissociation energies, of selected radicals and molecules and their cations obtained by pulsed field ionization photoion-photoelectron measurements and state-of-the-art thermochemical predictions calculated by the wavefunction-based ab initio CCSD(T)/CBS procedures with high-level corrections. The CCSD(T)/CBS method combines the coupled cluster approach including single, double, and quasi-perturbative triple excitations [CCSD(T)] and the complete basis set (CBS) extrapolation approximation. This benchmarking effort indicates that the CCSD(T)/CBS procedures together with high-level corrections are capable of yielding reliable thermochemical predictions with error limits ≤10 meV for small radicals and molecules and their cations. The error limits increase to ∼35 meV for larger molecular species, such as phenyl and benzyl radicals. © 2006 American Chemical Society.