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
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 = 10 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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عنوان ژورنال:
دوره 8 شماره
صفحات -
تاریخ انتشار 2017