Wave Packet Dynamics at an Extended Seam of Conical Intersection: Mechanism of the Light-Induced Wolff Rearrangement
Quantum dynamics calculations on a model surface based on CASPT(2)//CASSCF calculations are carried out to probe the traversal of a wave packet through an extended seam of conical intersection during the light-induced Wolff rearrangement of diazonaphtoquinone. The reaction is applied in the fabricat...
| Autores: | , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2012 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/11481 |
| Acceso en línea: | http://hdl.handle.net/10256/11481 |
| Access Level: | acceso embargado |
| Palabra clave: | Dinàmica molecular Molecular dynamics Espectroscòpia infraroja Infrared spectroscopy Rotació molecular Molecular rotation |
| Sumario: | Quantum dynamics calculations on a model surface based on CASPT(2)//CASSCF calculations are carried out to probe the traversal of a wave packet through an extended seam of conical intersection during the light-induced Wolff rearrangement of diazonaphtoquinone. The reaction is applied in the fabrication of integrated circuits. It consists of nitrogen elimination and ring rearrangement to yield a ketene. After excitation, the wave packet relaxes and reaches the extended seam. A fraction of the wave packet decays to the ground state at a region of the seam connected to a carbene intermediate, while the remaining part decays at a region leading to the ketene. The passage of the wave packet through the extended seam explains the competition between concerted ketene formation and a stepwise mechanism involving a carbene. The two primary photoproducts are formed in the first 100 fs of the simulation, in agreement with recent ultrafast spectroscopy measurements |
|---|