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Ultrafast relaxation and 2D IR of the aqueous trifluorocarboxylate ion
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Image of FIG. 1.
FIG. 1.

Experimental linear IR spectra. TFA-C12 (solid line, lower scale) and TFA-C13 (dashed line, upper scale) in . Inset shows the symmetric stretch band for both samples.

Image of FIG. 2.
FIG. 2.

Experimental linear IR spectra of TFA-C13 (open circles) in . The solid line is the fit with two Lorentzian functions (dashed and dotted lines).

Image of FIG. 3.
FIG. 3.

Pump-probe dynamics of TFA-C12 (a) and of TFA-C13 (b). Photoinduced transient signal (gray filled circles) and nonexponential fit (black line). The insets show the spectrally resolved signals at 0 fs delay between pump and probe.

Image of FIG. 4.
FIG. 4.

Experimental 2D IR vibrational echo spectra for population time , , and . Upper and lower rows correspond to TFA-C12 and TFA-C13, respectively, in .

Image of FIG. 5.
FIG. 5.

Schematic kinetic diagram for two/three coupled modes with an energy gap. The symmetric and asymmetric carboxylate stretches are denoted as and , respectively, and the combinational mode as . Dotted arrows represent the pathways added to the three level system for the modeling of TFA-C13.

Image of FIG. 6.
FIG. 6.

Slope vs population time for TFA-C12 (open circles) and TFA-C13 (filled circles). The smooth lines are the corresponding fits to Eqs. (5) and (6) using the parameters given in Table III.

Image of FIG. 7.
FIG. 7.

Autocorrelation of the frequency fluctuations calculated from the MD/DFT map. Open circles are the FFCF and the solid line is the fit of the correlation function with two exponentials.

Image of FIG. 8.
FIG. 8.

Relationship between pure dephasing parameters, and , and the value, , of the normalized FFCF obtained from the slope as defined in the text. (a) shows the possible pairs of and that fit the asymmetric stretch of the carboxylate for TFA-C12 for a given value of as discussed in the text. (b) depicts the normalized FFCF intercept at for the different pairs of and obtained in Fig. 8(a). The upper -axis of (b) displays the corresponding to the displayed in the lower axis. Insets in both Figures are zooms around the values for the parameters that fit the linear IR and the value of from the 2D IR spectrum of TFA-C12.

Image of FIG. 9.
FIG. 9.

Linear IR spectra of TFA-C12. The open circles are the experimental absorption line shape; the solid line is the fit to experimental parameters as discussed in the text relating to Eq. (7).

Image of FIG. 10.
FIG. 10.

Solvation shell configurations of TFA with the highest frequency deviations. Idealized solvent conformations for the maximum (a) and minimum (b) frequencies marked with arrows in the inset of Fig. 11. Hydrogen occupancy probability for all the solvent conformations in which the carboxylate asymmetric stretch frequency is calculated to be within 25% of the maximum (c) and 25% of the minimum (d). The transparent and solid isosurfaces of (c) and (d) represent the 66% and 99% probability of finding a hydrogen atom, respectively.

Image of FIG. 11.
FIG. 11.

Simulated frequency fluctuation of the asymmetric stretch mode. Inset shows a zoom of the marked area. Grey dots and solid black lines represent the frequency fluctuation and its window average, respectively. Dash black line is the average of the frequency fluctuation with respect to the gas phase value at .


Generic image for table
Table I.

Parameters of pump-probe dynamics fit for different temperatures and samples.

Generic image for table
Table II.

Parameters obtained from the global fitting of the TFA-C12 pump-probe kinetics at different temperatures. Parameters obtained from individual fits at different temperatures are shown in parenthesis.

Generic image for table
Table III.

Parameters of the experimental and theoretically predicted FFCFs. The experimental parameters extracted from experimental results and from a simultaneous fit of the linear absorption spectra and of slope of the 2D IR spectrum nodal contour line (marked with ).


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ultrafast relaxation and 2D IR of the aqueous trifluorocarboxylate ion