Femtosecond observation of benzyne intermediates in a molecular beam: Bergman rearrangement in the isolated molecule
AUTOR(ES)
Diau, Eric W.-G.
FONTE
The National Academy of Sciences
RESUMO
In this communication, we report our femtosecond real-time observation of the dynamics for the three didehydrobenzene molecules (p-, m-, and o-benzyne) generated from 1,4-, 1,3-, and 1,2-dibromobenzene, respectively, in a molecular beam, by using femtosecond time-resolved mass spectrometry. The time required for the first and the second C-Br bond breakage is less than 100 fs; the benzyne molecules are produced within 100 fs and then decay with a lifetime of 400 ps or more. Density functional theory and high-level ab initio calculations are also reported herein to elucidate the energetics along the reaction path. We discuss the dynamics and possible reaction mechanisms for the disappearance of benzyne intermediates. Our effort focuses on the isolated molecule dynamics of the three isomers on the femtosecond time scale.
ACESSO AO ARTIGO
http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=26440Documentos Relacionados
- Femtosecond direct observation of charge transfer between bases in DNA
- A brief comment on the dynamical behavior of a forced nonlinear slewing beam: 1. Superharmonic resonance
- Evaluation of titanium implants with surface modification by laser beam: biomechanical study in rabbit tibias
- Observation of an A-DNA to B-DNA transition in a nonhelical nucleic acid hairpin molecule using molecular dynamics.
- Direct observation of vibrational coherence in bacterial reaction centers using femtosecond absorption spectroscopy.
