Contribution in an anthology

Authors list: Bettinger, Holger F; Schleyer, Paul v. R.; Schreiner, Peter R.

Appeared in: Modern electronic structure theory and applications in organic chemistry

Editor list: Davidson, Ernest R

Publication year: 1997

Pages: 89-171

ISBN: 978-981-02-3168-2

eISBN: 978-981-4497-31-2

DOI Link: https://doi.org/10.1142/9789812839756_0003

Abstract: 

The application of ab initio and density functional theory (DFT) to selected problems in carbene chemistry is reviewed. A brief historic introduction is followed by an analysis of the theoretical techniques necessary to describe carbene structures and properties adequately. An evaluation of the computational methods {self-consistent field (SCF), nth order Møller-Plesset (MPn), complete active space (CAS), multireference configuration interaction (MR-CISD), coupled cluster (CC), full configuration interaction (FCI), and DFT} as well as basis set dependencies is presented. Most notably, hybrid Hartree–Fock/DFT results (B3LYP, in conjunction with moderate basis sets, e.g., triple-ζ (TZ) plus polarization) are reasonably close in quality to highest level treatments {e.g., CCSD(T)/TZ2P}, at much lower computational costs. The usual problems associated with pure Hartree-Fock based methods, such as spin contamination, are much less pronounced at hybrid Hartree–Fock/DFT levels. The structures, properties, and reactions of simple alkyl (methylene, ethylidene, dimethylcarbene, 2–butylidene, and tert.-butylcarbene), cyclic (parent as well as substituted cyclopropylidenes, cyclobutylidene, cyclopentadienylidene, and cyclopenta-1,3-dien-5-yl carbene), unsaturated (vinylcarbene, vinylidene, propynylidene, and propadienylidene), and aromatic carbenes (phenyl- and naphthylcarbene) are presented systematically.

Harvard Citation style: Bettinger, H., Schleyer, P. and Schreiner, P. (1997) Computational Analyses of Prototype Carbene Structures and Reactions, in Davidson, E. (ed.) Modern electronic structure theory and applications in organic chemistry. Singapore: World Scientific, pp. 89-171. https://doi.org/10.1142/9789812839756_0003

APA Citation style: Bettinger, H., Schleyer, P., & Schreiner, P. (1997). Computational Analyses of Prototype Carbene Structures and Reactions. In Davidson, E. (Ed.), Modern electronic structure theory and applications in organic chemistry (pp. 89-171). World Scientific. https://doi.org/10.1142/9789812839756_0003