Unravelling the mechanisms of vibrational relaxation in solution† †All experimental data are archived in the University of Bristol's Research Data Storage Facility (DOI: 10.5523/bris.2vk036f35m5aq2dnlb79c0wcsh). ‡ ‡Electronic supplementary information (ESI) available: Further discussion of spectral lineshapes, concentration dependence of transient absorption data, theoretical calculations, IR-pump IR-probe spectra, transient absorption spectra including animation of spectra. See DOI: 10.1039/c6sc05234g Click here for additional data file. Click here for additional data file.

نویسندگان

  • Michael P. Grubb
  • Philip M. Coulter
  • Hugo J. B. Marroux
  • Andrew J. Orr-Ewing
  • Michael N. R. Ashfold
چکیده

Large solute translational energy leads to homogeneous line broadening in transient spectra due to the increased frequency of perturbing interactions with the solvent cage. Furthermore small solute rotation has been shown to be relatively unhindered in perfluorocarbon (PFC) solutions, leading to the observation of significant P and R rotational band structure in the absorption spectrum. Indeed the final equilibrated lineshape of the NO2 3 = 10 transition cannot be fit with a single Voigt profile. The initial homogeneous linewidth of the NO2 transitions following N2O4 photolysis in perfluorohexane solution is approximately 39 cm-1, and narrows to its final width of 15.6 ± 0.3 cm-1 after about 5 ps. This timescale is consistent with previously measured rotational / translational energy relaxation in perfluorohexane.1

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منابع مشابه

5,20-Bis(α-oligothienyl)-substituted [26]hexaphyrins possessing electronic circuits strongly perturbed by meso-oligothienyl substituents† †Electronic supplementary information (ESI) available: General experimental methods, HR-ESI-TOF mass spectra, UV/Vis absorption spectra, NMR spectra, cyclic voltammograms, X-ray crystal structures and results of DFT calculations. CCDC 1025770, 1025771 and 1025772. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03394a Click here for additional data file. Click here for additional data file.

Department of Chemistry, Graduate Schoo Kyoto 606-8502, Japan. E-mail: osuka@kuc Spectroscopy Laboratory for Functional p Chemistry Yonsei University, Seoul 120-749 † Electronic supplementary information methods, HR-ESI-TOF mass spectra, UV cyclic voltammograms, X-ray crystal struc CCDC 1025770, 1025771 and 1025772. Fo or other electronic format see DOI: 10.103 Cite this: Chem. Sci., 2015, 6, 1696

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عنوان ژورنال:

دوره 8  شماره 

صفحات  -

تاریخ انتشار 2017