Hybrid Atomic Orbitals in Organic Chemistry. Part 1: Critique of Formal Aspects

Lamoureux, Guy; Ogilvie, J. F.

doi:10.21577/0100-4042.20170376

Cited by 4 publications

(3 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In addition, the use of the sp 3 hybrid orbitals for the carbon atom in methane accounted for the tetravalence of the carbon atom and the tetrahedral structure of the molecule. Despite the ubiquitous use of hybrid orbitals in chemical thinking, there were early concerns about the use of hybrid orbitals, and more recently there has been a spirited discussion in the chemistry education literature about the role of hybrid orbitals in the chemistry curriculum − (see also refs and ).…”

Section: Insights Into the Electronic Structure Of Moleculesmentioning

confidence: 99%

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Dunning

Cooper

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

Spin-Coupled Generalized Valence Bond (SCGVB) theory provides the foundation for a comprehensive theory of the electronic structure of molecules. SCGVB theory offers a compelling orbital description of the electronic structure of molecules as well as an efficient and effective zero-order wave function for calculations striving for quantitative predictions of molecular structures, energetics and other properties. The orbitals in the SCGVB wave function are usually semi-localized and, for most molecules, can be interpreted using concepts familiar to all chemists (hybrid orbitals, localized bond pair, lone pairs, etc.). SCGVB theory also provides new perspectives on the nature of the bonds in molecules such as C2, Be2 and SF4/SF6. SCGVB theory contributes unparalleled insights into the underlying cause of the first-row anomaly in inorganic chemistry as well as the electronic structure of organic molecules and the electronic mechanisms of organic reactions. The SCGVB wave function accounts for nondynamical correlation effects and, thus, corrects the most serious deficiency in molecular orbital (RHF) wave functions. Dynamical correlation effects, which are critical for quantitative predictions, can be taken into account using the SCGVB wave function as the zero-order wave function for multireference configuration interaction or coupled cluster calculations.* In prior articles in the literature the Spin-Coupled Generalized Valence Bond wave function has usually been referred to as the Spin-Coupled Valence Bond (SCVB) wave function or the full Generalized Valence Bond (full GVB) wave function. These wave functions are identical; to prevent confusion, the authors have adopted the allencompassing SCGVB name. Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds3 and recoupled pair bond dyad. 36 The SCGVB wave function describes molecules in terms of orbitals that are optimized at each geometry, allowing the atomic orbitals to change as a result of molecule formation. In addition to the changes in the orbitals, optimization of the general spin function used in the SCGVB wave function allows the spin function to change from that appropriate for the separated atoms or fragments to that appropriate for the molecule. SCGVB theory addresses a major limitation of RHF theory, providing an excellent zero-order description of molecules that require multiconfiguration descriptions, the making/breaking of bonds, and many chemical reactions and excited states. For most molecules, the SCGVB wave function captures the essential features of the FORS/CASSCF wave functions, with much reduced complexity compared to these latter wave functions.

show abstract

Section: Insights Into the Electronic Structure Of Moleculesmentioning

confidence: 99%

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Dunning

Cooper

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…We explain elsewhere that hybrids and hybridization models to explain molecular shapes are redundant. 41 We provide there also a simple solution to the problem of explaining molecular shapes --remove the explanation and simply provide the three-dimensional structure as an experimental fact. Once the structure is shown, what can one predict from it?…”

Section: • V Elimination Of the Traditional Use Of Orbitals In Futurementioning

confidence: 99%

General Chemistry Without Orbitals

Lamontagne

Ogilvie²

2020

Preprint

Self Cite

View full text Add to dashboard Cite

We illustrate the solutions of Schroedinger's equation for the hydrogen atom in coordinates of all four systems, and differentiate the applicability of orbitals in these four systems. We present reasons that future textbooks of general chemistry should exclude orbitals and discuss the teaching of general chemistry on this basis. The incompatibility of molecular structure and quantum mechanics is discussed before a conclusion that quantum mechanics and its orbital artifacts are irrelevant for general chemistry.

show abstract

“…2) Polarizability (of atom or group directly connected to acidic or basic site 3) Geometry (bond angles around atom connected to acidic or basic site) 21 4) Delocalization (conjugated pi system in substrate or conjugate base) 5) Aromaticity (presence of aromaticity or anti-aromaticity in substrate or conjugate base) 6) Inductive effects (donation, withdrawal, or neutral effects of atom or group connected via sigma system to acidic or basic site) 7) Resonance effects (donation, withdrawal, or neutral effects of atom or group connected via pi system to acidic or basic site)…”

Section: • Effect Of Substituents On Reactivity Of Benzoic Acidsmentioning

confidence: 99%

Grids to Illustrate Induction and Resonance Effects: Aromatic Acidity and Basicity

Lamoureux

Árias-Alvarez²

2020

Preprint

Self Cite

View full text Add to dashboard Cite

The effect of substituents on the acidity of benzoic acids and anilines has been organized in grids to demonstrate the inductive and resonance effects. The relation between structure and pKa is emphasized by a new educational process: the Search-Organize-Predict (SOP) procedure. • KEYWORDSAdvanced undergraduate, organic chemistry for chemistry majors, acid/base chemistry, resonance effects, inductive effects, benzoic acid, aniline

show abstract

Hybrid Atomic Orbitals in Organic Chemistry. Part 1: Critique of Formal Aspects

Cited by 4 publications

References 22 publications

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

General Chemistry Without Orbitals

Grids to Illustrate Induction and Resonance Effects: Aromatic Acidity and Basicity

Contact Info

Product

Resources

About