Journal article
Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study
The Journal of chemical physics, Vol.144(12), pp.124311-124311
03/28/2016
DOI: 10.1063/1.4944930
PMID: 27036452
Abstract
Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH2 =CHCH2I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground (2P3/2, I) and spin-orbit excited (2P1/2, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N4/5 edge (45–60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive n
Iσ∗
C—I excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ∗ states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ∗(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs–65 fs and decay completely by 145 fs–185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic structure in the transition state region. The results provide a benchmark for theoretical calculations on the nature of core-excited states in halogenated hydrocarbons, especially in the transition state region along the C—I reaction coordinate.
Details
- Title: Subtitle
- Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study
- Creators
- Aditi Bhattacherjee - 3Department of Physics, University of California, Berkeley, California 94720, USAAndrew R Attar - 3Department of Physics, University of California, Berkeley, California 94720, USAStephen R Leone - 3Department of Physics, University of California, Berkeley, California 94720, USA
- Resource Type
- Journal article
- Publication Details
- The Journal of chemical physics, Vol.144(12), pp.124311-124311
- DOI
- 10.1063/1.4944930
- PMID
- 27036452
- ISSN
- 0021-9606
- eISSN
- 1089-7690
- Number of pages
- 10
- Grant note
- EEC-0310717 / NSF ERC, EUV Science and Technology DE-AC02-05CH11231 / U.S. Department of Energy (DOE) (http://dx.doi.org/10.13039/100000015)
- Language
- English
- Date published
- 03/28/2016
- Academic Unit
- Chemistry
- Record Identifier
- 9984216595402771
Metrics
14 Record Views