Chemical structures of OF2 and OF3.
Effects of varying the vibrational ground- and excited-state vibrational frequencies (a), excited-state displacement (b), and homogeneous linewidth (c) in a one-mode model of the absorption spectrum as described in Sec. II B. In panel (a), the solid line represents the calculation where the frequency is kept at for both ground and excited state, while the dotted line corresponds to different ground and excited-state frequencies . In panel (b), the frequencies are kept the same at . The solid line represents the spectrum obtained with a small displacement and the dotted line the case with moderate displacement . In panel (c), all the parameters are kept the same except for the homogeneous linewidth. The dotted line represents the effect of a fivefold increase in the , while the gray line uses a second mode at low frequency to reproduce the broadening of the spectrum. All other parameters in the calculations are the same for all the calculations.
(a) Ground-state absorption spectra of OF2 (closed triangles) and OF3 (open circles). (b) Corresponding excited-state absorption spectra.
Absorption transients of OF2 (a) and OF3 (b) at various probe photon energies, indicated in the insets.
Simulation of the ground-state (a) and excited-state (b) absorption spectra of OF2. The parameters used in the simulation are reported in Table I.
Simulation of the ground-state (a) and excited-state (b) absorption spectra of OF3. The parameters used in the simulation are reported in Table I.
Transition energy as a function of inverse number of phenyl rings constituting the oligomer (left axis). The data for the dimer and trimer are obtained from Table I. The data point at (with the large -axis incertitude) corresponds to a PF derivative, taken from Ref. 6. Also shown is the ratio of excited state to ground-state transition energies (right axis).
Model parameters for the ground-state and excited-state absorption spectra of OF2 and OF3 using the time-dependent formalism described in Sec. II B. Parameter uncertainties are determined by visual comparison of the model results and the experimental data.
Total reorganization energies determined from Eq. (14) and Table I.
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