dc.contributor.author | Hayes, Sophia C. | en |
dc.contributor.author | Philpott, M. P. | en |
dc.contributor.author | Mayer, S. G. | en |
dc.contributor.author | Reid, P. J. | en |
dc.creator | Hayes, Sophia C. | en |
dc.creator | Philpott, M. P. | en |
dc.creator | Mayer, S. G. | en |
dc.creator | Reid, P. J. | en |
dc.date.accessioned | 2019-11-21T06:19:20Z | |
dc.date.available | 2019-11-21T06:19:20Z | |
dc.date.issued | 1999 | |
dc.identifier.issn | 1089-5639 | |
dc.identifier.uri | http://gnosis.library.ucy.ac.cy/handle/7/55544 | |
dc.description.abstract | The photochemistry of chlorine dioxide (OClO) in water and acetonitrile is investigated using time-resolved resonance Raman spectroscopy. Stokes and anti-Stokes spectra are measured as a function of time following photoexcitation using degenerate pump and probe wavelengths of 390 nm. For aqueous OClO, the time-dependent Stokes intensities are found to be consistent with the re-formation of ground-state OClO by subpicosecond geminate recombination of the primary ClO and O photofragments. This represents the first unequivocal demonstration of primary-photoproduct geminate recombination in the condensed-phase photochemistry of OClO. Anti-Stokes intensity corresponding to the OClO symmetric stretch is observed demonstrating that, following geminate recombination, excess vibrational energy is deposited along this coordinate. Analysis of the anti-Stokes decay kinetics demonstrates that, in water, intermolecular vibrational relaxation occurs with a time constant of ∼9 ps. For OClO dissolved in acetonitrile, the Stokes scattering intensities are consistent with a significant reduction in the geminate-recombination quantum yield relative to water. Comparison of the OClO anti-Stokes decay kinetics in acetonitrile and water demonstrates that the rate of intermolecular vibrational relaxation is ∼4 times smaller in acetonitrile. Finally, in both solvents the appearance of symmetric-stretch anti-Stokes intensity is significantly delayed relative to geminate recombination. This delay is consistent with the initial deposition of excess vibrational energy along the asymmetric-stretch coordinate followed by intramolecular vibrational energy redistribution. The time scale for this redistribution is ∼5 ps in water and ∼20 ps in acetonitrile suggesting that intramolecular vibrational energy reorganization is solvent dependent. | en |
dc.source | Journal of Physical Chemistry A | en |
dc.source.uri | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0001035226&partnerID=40&md5=c5b74787f05a63c631a1a23612263cbe | |
dc.title | A Time-Resolved Resonance Raman Study of Chlorine Dioxide Photochemistry in Water and Acetonitrile | en |
dc.type | info:eu-repo/semantics/article | |
dc.description.volume | 103 | |
dc.description.issue | 28 | |
dc.description.startingpage | 5534 | |
dc.description.endingpage | 5546 | |
dc.author.faculty | 002 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied Sciences | |
dc.author.department | Τμήμα Χημείας / Department of Chemistry | |
dc.type.uhtype | Article | en |
dc.description.notes | <p>Cited By :37</p> | en |
dc.source.abbreviation | J Phys Chem A | en |
dc.contributor.orcid | Hayes, Sophia C. [0000-0002-2809-6193] | |
dc.gnosis.orcid | 0000-0002-2809-6193 | |