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For 12 C in scCO2, the change of temperature over 308-332 K at constant density (reduced density pr, p/pc, 1.36) resulted in a small shift of 164 cm-1, 2.5 nm, see Supporting Information Table S1 (e, Almost no thermochromic shift was observed for 12 C in scCF3H over the temperature range 308-333 K at constant density (pr, 1.70, see Supporting Information Table S1 (h, In the case of 8 C, thermochromic shifts of 224 cm-1, 4.1 nm) in scCO2 over the temperature range 309-333 K at the constant density pr, 1.29 (see Supporting Information Table S2 (e, and of 220 cm-1, 4.2 nm) in scCF3H at the constant density pr, 1.70 over the temperature range 308-334 K (see Supporting Information Table S2 h, were observed
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A separation into two distinct populations might appear artificial from a physical standpoint and partly stems from the suggestive nature of the biexponential fit of the decay. We note that the decay of the transient absorption profiles in CF3H could also be well described by using a stretched-exponential term instead of the first two exponential terms in eq 7, leading to 1(t, A0, A1 exp(, t, t0)/t1]y+ A3 exp(-(t, t0, r3, 0.5(l, erf{(t, t0, √2σ), Here, the parameter Y (<1) in the first term merely describes the departure from monoexponential behavior. Such an approach (requiring one parameter less than eq 7) has been frequently used in the absence of a theoretical model to describe the relaxation of solute molecules, which are sampling different types of mieroenvironme
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0)/(√2σ)}). Here, the parameter Y (<1) in the first term merely describes the departure from monoexponential behavior. Such an approach (requiring one parameter less than eq 7) has been frequently used in the absence of a theoretical model to describe the relaxation of solute molecules, which are sampling different types of mieroenvironments within a solvent [Arzhantsev et al. J. Phys. Chem. B 2007, 111, 4978;
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