Abstract
Abstract The entire set of methyl anions, XCH 2 − , substituted by first‐row substituents, Li, BeH, BH 2 , CH 3 , NH 2 , OH, and F, was examined at various ab initio levels. Diffuse orbital‐augmented basis sets, such as 4−31+ G and 6−31+ G *, are needed to describe the energies of these anions adequately. Estimates of proton affinities are further improved by second‐order Møller–Plesset ( MP 2) electron correlation corrections, but relative energies are less affected. The methyl group in the ethyl anion is destabilizing, the amino substituent is borderline, but all other groups are stabilizing. Very large π effects are exhibited by BH 2 and BeH groups; inductive stabilization by the electronegative F and OH groups is less effective. Lithium also is stabilizing, but the best singlet geometry of CH 2 Li − is not planar. A planar CH 2 Li − triplet with a π 1 configuration may be lower in energy.
Keywords
ChemistrySubstituentSinglet stateIonBasis setAb initioLithium (medication)Computational chemistryGaussian orbitalCrystallographyElectronic correlationGroup (periodic table)Ab initio quantum chemistry methodsStereochemistryDensity functional theoryMoleculeAtomic physicsOrganic chemistryPhysics
Affiliated Institutions
Related Publications
Integrated spatial electron populations in molecules: Application to simple molecules
Abstract The electron projection function P ( x , z ) = ∫ ρ( x , y , z ) dy is used to evaluate charge transfer and covalency in two series of molecules, LiX and CH 3 X (X = Li,...
Self-Consistent Procedures for Generalized Valence Bond Wavefunctions. Applications H3, BH, H2O, C2H6, and O2
Methods of efficiently optimizing the orbitals of generalized valence bond (GVB) wavefunctions are discussed and applied to LiH, BH, H3, H2O, C6H6, and O2. The strong orthogonal...
Natural population analysis
A method of ‘‘natural population analysis’’ has been developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis se...
Gaussian-2 theory for molecular energies of first- and second-row compounds
The Gaussian-2 theoretical procedure (G2 theory), based on ab initio molecular orbital theory, for calculation of molecular energies (atomization energies, ionization potentials...
Nucleophilic Degradation of Fenitrothion Insecticide and Performance of Nucleophiles: A Computational Study
Ab initio and density functional theory (DFT) calculations have been performed to understand the destruction chemistry of an important organophosphorus insecticide O,O-dimethyl ...
Publication Info
- Year
- 1982
- Type
- article
- Volume
- 3
- Issue
- 3
- Pages
- 363-371
- Citations
- 263
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
263
OpenAlex
Cite This
Günther W. Spitznagel,
Timothy Clark,
Jayaraman Chandrasekhar
et al.
(1982).
Stabilization of methyl anions by first‐row substituents. The superiority of diffuse function‐augmented basis sets for anion calculations.
Journal of Computational Chemistry
, 3
(3)
, 363-371.
https://doi.org/10.1002/jcc.540030311
Identifiers
- DOI
- 10.1002/jcc.540030311