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Ultrafast dynamics of aniline in the 294-234 nm excitation range: the role of the πσ∗ state
- Source :
- The Journal of chemical physics. 135(5)
- Publication Year :
- 2011
-
Abstract
- The ultrafast relaxation of jet-cooled aniline was followed by time-resolved ionization, after excitation in the 294-234 interval. The studied range of energy covers the absorption of the two bright ππ∗ excitations, S(1) and S(3), and the almost dark S(2) (πσ∗) state. The employed probe wavelengths permit to identify different ultrafast time constants related with the coupling of the involved electronic surfaces. A τ(1) = 165 ± 30 fs lifetime is attributed to dynamics along the S(2) (πσ∗) repulsive surface. Other relaxation channels as the S(1)→S(0) and S(3)→S(1) internal conversion are also identified and characterized. The work provides a general view of the photophysics of aniline, particularly regarding the role of the πσ∗ state. This state appears as minor dissipation process due to the ineffective coupling with the bright S(1) and S(3) states, being the S(1)→S(0) internal conversion the main non-radiative process in the full studied energy range. Additionally, the influence of the off-resonance adiabatic excitation of higher energy electronic states, particularly S(3), is also observed and discussed.
- Subjects :
- Range (particle radiation)
Aniline Compounds
Chemistry
General Physics and Astronomy
Electrons
Internal conversion (chemistry)
Photochemical Processes
Photoexcitation
Ionization
Relaxation (physics)
Quantum Theory
Physical and Theoretical Chemistry
Atomic physics
Absorption (electromagnetic radiation)
Adiabatic process
Excitation
Subjects
Details
- ISSN :
- 10897690
- Volume :
- 135
- Issue :
- 5
- Database :
- OpenAIRE
- Journal :
- The Journal of chemical physics
- Accession number :
- edsair.doi.dedup.....1ea063cf661f34b17727ebd7756f3783