A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons

Fukui, Kenichi; Yonezawa, Teijiro; Shingu, Haruo

doi:10.1142/9789812795847_0001

Cited by 54 publications

(68 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[19] Molecular Orbital (MO) theory has been very useful and successful for the theoretical analysis of chemical reactions and chemical reactivity. The frontier orbital theory [20] and the orbital symmetry rules of Woodward and Hoffman [21] are paradigmatic examples of the possibilities of quantum chemistry within the MO theory.…”

Section: Historical Frameworkmentioning

confidence: 99%

A Complete NCI Perspective: From New Bonds to Reactivity

Narth¹,

Maroun²,

Boto³

et al. 2016

Challenges and Advances in Computational Chemistry and Physics

View full text Add to dashboard Cite

The Non-Covalent Interaction (NCI) index is a new topological tool that has recently been added to the theoretical chemist's arsenal. NCI fills a gap that existed within topological methods for the visualization of non-covalent interactions. Based on the electron density and its derivatives, it is able to reveal both attractive and repulsive interactions in the shape of isosurfaces, whose color code reveals the nature of the interaction. It is interesting to note that NCI can even be calculated at the promolecular level, making it a suitable tool for big systems, such as proteins or DNA. Within this chapter we will review the main characteristics of NCI, its similarities with and differences from previous approaches. Special attention will be paid to the visualization of new interaction types. Being based on the electron density, NCI is not only very stable with respect to the calculation method, but it is also a suitable tool for detecting new bonding mechanisms, since all such mechanisms should have a detectable effect on the electron density. This type of approach overcomes the limitations of bond definition, revealing all interaction types, irrespective of whether they have a name or have previously been identified. Finally, we will show how this tool can be used to understand chemical change along a chemical reaction. We will show several examples of torquoselectivity and put forward an explanation of selectivity based on secondary interactions which is complementary to the historical orbital approach.A complete NCI perspective: from new bonds to reactivity 3

show abstract

Section: Historical Frameworkmentioning

confidence: 99%

A Complete NCI Perspective: From New Bonds to Reactivity

Narth¹,

Maroun²,

Boto³

et al. 2016

Challenges and Advances in Computational Chemistry and Physics

View full text Add to dashboard Cite

show abstract

“…The situation can be simplified further by considering only the frontier orbitals [42], i.e. the HOMO of one system and the LUMO of the other one.…”

Section: Reactionsmentioning

confidence: 99%

A Graph-Based Toy Model of Chemistry

Benkö

Flamm

Stadler

2003

J. Chem. Inf. Comput. Sci.

View full text Add to dashboard Cite

Large scale chemical reaction networks are a ubiquitous phenomenon, from the metabolism of living cells to processes in planetary atmospheres and chemical technology. At least some of these networks exhibit distinctive global features such as the "small world" behavior. The systematic study of such properties, however, suffers from substantial sampling biases in the few networks that are known in detail. A computational model for generating them is therefore required. Here we present a Toy Model that provides a consistent framework in which generic properties of extensive chemical reaction networks can be explored in detail and that at the same time preserves the "look-and-feel" of chemistry: Molecules are represented as labeled graphs, i.e., by their structural formulae; their basic properties are derived by a caricature version of the Extended Hückel MO theory that operates directly on the graphs; chemical reaction mechanisms are implemented as graph rewriting rules acting on the structural formulae; reactivities and selectivities are modeled by a variant of the Frontier Molecular Orbital Theory based on the Extended Hückel scheme. The approach is illustrated for two types of reaction networks: Diels-Alder reactions and the formose reaction implicated in prebiotic sugar synthesis.

show abstract

“…The energy levels of electrons and their gaps provide useful data for implications on the reactivity of the active sites [79,82,83] according to the frontier molecular orbital (FMO) theory [84]. Table 5 reports the HOMO and LUMO levels and HOMO-LUMO energy gaps for the optimized clusters shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Theoretical identification of structural heterogeneities of divalent nickel active sites in NiMCM-41 nanoporous catalysts

2016

View full text Add to dashboard Cite

This paper deals with the theoretical identification of the digrafted Ni species exchanged into the defect sites of MCM-41 using hybrid density functional theory. The nickel-siloxane clusters included seven 2T-6T rings. The 2MR and 5MR structures were found to be the least and most favorable sites to form thermodynamically. The Ni-O distances ranged from 1.69 to 1.79 Å with the highest asymmetry found in 5MR. The 4MR and 5MR clusters showed also interesting intertwined nickel configurations. Overall, the QTAIM calculations revealed the transient electrostatic nature of the Ni-O bonds.

show abstract

A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons

Cited by 54 publications

References 0 publications

A Complete NCI Perspective: From New Bonds to Reactivity

A Complete NCI Perspective: From New Bonds to Reactivity

A Graph-Based Toy Model of Chemistry

Theoretical identification of structural heterogeneities of divalent nickel active sites in NiMCM-41 nanoporous catalysts

Contact Info

Product

Resources

About