Role of frontier orbitals in chemical reactions.

@article{Fukui1982RoleOF,
  title={Role of frontier orbitals in chemical reactions.},
  author={Ken-ichi Fukui},
  journal={Science},
  year={1982},
  volume={218 4574},
  pages={
          747-54
        }
}
  • K. Fukui
  • Published 19 November 1982
  • Chemistry
  • Science
Since the 3rd century for more than a thousand years chemistry has been thought of as a complicated, hard-to-predict science. Efforts to improve even a part of its unpredictable character are said to have born fruit first of all in the success of the " electronic theory ". This was founded mainly by organic chemists , such as Fry, Stieglitz, Lucas, Lapworth and Sidgwick, brought to a completed form by Robinson and Ingold, and developed later by many other chemists. 1 In the electronic theory… 

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References

SHOWING 1-10 OF 137 REFERENCES

Conservation of orbital symmetry

Chemistry remains an experimental science. The theory of chemical bonding leaves much to be desired. Yet, the past 20 years have been marked by a fruitful symbiosis of organic chemistry and molecular

Molecular Orbital Theory of Orientation in Aromatic, Heteroaromatic, and Other Conjugated Molecules

As to the LCAO MO treatment of the orientation problem in chemical reactions of π‐electron systems, the frontier electron concept which has been previously introduced by the authors for explaining

Symmetry, topology, and aromaticity

The 4q + 2 T-electron prerequisite for cyclic stabilization is shown to be a necessary consequence whenever orbitals of ir symmetry are constrained to interact within a pericyclic topology.

Physical Organic Chemistry:

IN the preface to this volume Prof. Hammett truly says: “It is one of the commonest occurrences in the development of science that the necessary subdivision of the subject leads to a temporary

Theory of Substitution in Conjugated Molecules

A theory concerning the mechanism of substitution in conjugated molecules is stated. The energy of the whole system is divided into σ- and π-parts. When certain relations hold between some integrals

A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons

In the search for a quantitative correlation between reactivity and electronic configuration of aromatic hydrocarbons, the electron density, at each carbon atom, of the highest occupied π‐orbital in

The electronic structure of conjugated systems I. General theory

It is shown that the mutual polarizability of two atoms or two bonds or an atom and a bond is important in determining the effect of structural changes on chemical reactivity, and also in calculating force constants and interaction terms for the vibration of bonds.

Quantum theory of molecular electronic structure

With the increasing availability of powerful computers, attempts to calculate the electronic structure and properties of molecules by the direct ab initio solution of a many-body Schrodinger equation

A Molecular Orbital Calculation of Chemically Interacting Systems. Addition of Singlet Methylene to Ethylene

A semi-empirical self-consistent-field molecular orbital calculation of the addition of singlet methylene to ethylene was carried out on the basis of an isolated molecule approximation. The
...