Repozytorium

The joint use of catastrophe theory and electron localization function to characterize molecular mechanisms. A density functional study of the Diels-Alder reaction between ethylene and 1,3-butadiene.

Autorzy

Sławomir Berski

Juan Andrés

Bernard Silvi

Luis R. Domingo

Rok wydania

2003

Czasopismo

Journal of Physical Chemistry A

Numer woluminu

107

Strony

6014-6024

DOI

10.1021/jp030272z

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The catastrophe theory has been used to investigate the reorganization of the localization basins, within the electron localization function formalism, along the intrinsic reaction coordinate associated with the reaction pathway of the Diels−Alder reaction between ethylene and 1,3-butadiene. There are distinguished seven phases (I−VII) characterized by a decay and formation of the double bonds, an accumulation of the nonbonding electron density on the C atoms involved in the formation of two sigma bonds and a ring closure processes. During the reaction 10 catastrophes occur belonging to two elementary types:  fold and cusp. The transition structure is located in phase III, being determined by a “reduction” of the double CC bond of ethylene to the single bond, and it is not associated with any special event on the intrinsic reaction coordinate path. For the first time, it is shown that formation of two new sigma C−C bonds between ethylene and 1,3-butadiene begins in phase VI at 2.044Å.

Słowa kluczowe

Chemical reactions, Electron density, Hydrocarbons, Mathematical methods, Molecules

Adres publiczny

https://doi.org/10.1021/jp030272z

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

Podobne publikacje
2004

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(OH)2- with H2O and O2.

Sambrano J. R., Gracia L., Andrés Juan, Berski Sławomir, Beltrán A.