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Carbocations

Carbocations

Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...

Valence Bond Theory

Valence Bond Theory

Overview of Valence Bond Theory

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

π Molecular Orbitals of the Allyl Cation and Anion

π Molecular Orbitals of the Allyl Cation and Anion

An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with an...

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Molecular Orbital Theory II

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π Molecular Orbitals of 1,3-Butadiene

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Conjugated dienes have lower heats of hydrogenation than cumulated and isolated dienes, making them more stable. The enhanced stabilization of conjugated systems can be understood from their π molecular orbitals.
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...

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Related Experiment Video

Updated: Jul 5, 2026

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

Published on: March 16, 2020

Carbene proton attachment energies: theoretical study.

Alexander Azenkeng¹, Jason D Laumb, Robert R Jensen

¹Department of Chemistry, University of North Dakota, P. O. Box 9024, Grand Forks, North Dakota 58202, USA.

The Journal of Physical Chemistry. A

|May 22, 2008

Summary

This study identifies a cost-effective computational method, MPW3LYP/6-311+G(d,p), for accurately calculating the energies and structures of carbenes and carbenium ions, crucial for hydrocarbon research.

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Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

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Probe Type II Band Alignment in One-Dimensional Van Der Waals Heterostructures Using First-Principles Calculations

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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Published on: April 8, 2020

Area of Science:

Computational Chemistry
Quantum Chemistry
Theoretical Chemistry

Background:

Carbenes and carbenium ions are reactive intermediates with significant roles in organic chemistry.
Accurate computational methods are needed to study their properties, but high-level calculations can be computationally expensive.

Purpose of the Study:

To evaluate and recommend a low-cost, accurate computational protocol for studying singlet carbenes and their corresponding carbenium ions.
To provide accurate thermochemical data for specific carbene species, including those not previously studied with ab initio methods.

Main Methods:

Employed various density functional theory (DFT) variants and second-order Møller-Plesset perturbation theory (MP2).
Utilized G3 theory and coupled cluster with singles and doubles, and perturbative triples (CCSD(T)) for benchmark comparisons.
Calculated geometries, electronic energies, and harmonic vibrational frequencies.

Main Results:

The MPW3LYP/6-311+G(d,p) DFT method showed excellent agreement with G3 results for proton attachment energies (PAEs), with a mean absolute deviation (MAD) of 1.76 kcal/mol.
Geometries calculated by MPW3LYP/6-311+G(d,p) closely matched MP2 results, with low MADs for bond lengths (0.005 Å) and angles (1.0°).
Vibrational frequencies confirmed true minima and provided data for zero-point corrected energies.

Conclusions:

The MPW3LYP/6-311+G(d,p) protocol offers a computationally efficient and accurate approach for thermochemical data of hydrocarbons and hydrocarbon cations.
This recommended method provides a valuable framework for studying coal-mimetic species and other moderate-sized organic molecules.