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Vibrational dynamics of a non-degenerate ultrafast rotor: The (C12,C13)-oxalate ion
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10.1063/1.4826137
/content/aip/journal/jcp/139/16/10.1063/1.4826137
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/16/10.1063/1.4826137

Figures

Image of FIG. 1.
FIG. 1.

Oxalate geometry and the vibrational energy levels in the asymmetric stretch region. (a) and (b) energy diagram of two coupled vibrational transitions.

Image of FIG. 2.
FIG. 2.

Synthetic scheme used to prepare C13-oxalate.

Image of FIG. 3.
FIG. 3.

FTIR spectra of ∼0.1 M solution of C13-oxalate ion in DO with solvent background subtracted. The open circles represent the experimental data points, whereas the line represents a model fit with Voigt profiles. The solid black line represents the fit and the dotted red and dashed green lines are its individual components.

Image of FIG. 4.
FIG. 4.

Experimental pump-probe signals of the C13-oxalate ion. Top panel shows parallel polarization (XXXX) pump-probe spectra of 0.1 M oxalate ion in water at T = 0.35 ps. The middle and lower panels show the isotropic signal of the low frequency at photo-induced absorption band (1518 cm−1) and the high frequency at bleach band (1590 cm−1), respectively. Black open squares correspond to the experimental data and the red line to the fitting described in the text.

Image of FIG. 5.
FIG. 5.

Experimental anisotropy dynamics of oxalate ion. Anisotropy of the low frequency at the new absorption band at 1518 cm−1 (top panel) and the high frequency at bleach/SE band at 1590 cm−1 (lower panel). Solid black lines correspond to the experimental data, and solid red and dashed blue are the fitted curves as described in the text.

Image of FIG. 6.
FIG. 6.

Absorptive 2D IR spectra of C13-oxalate ion in DO. 2D IR spectra for the XXXX (left column) and XXYY (right column) pulse polarizations at different waiting times: = 0, 0.45, 1.5, and 2.15 ps. Black dashed line corresponds to the diagonal (ω = ω).

Image of FIG. 7.
FIG. 7.

Vibrational population transfer of C13-oxalate in water. Experimental HTG signal for the ⟨XXXX⟩–3⟨XXYY⟩ in the cross-peak region at: 1510 cm−1 (top panel) and 1590 cm−1 (bottom panel). Open squares correspond to the experimental data and the red line to the fit with Eqs. (14) and (15) .

Image of FIG. 8.
FIG. 8.

Slope versus waiting time for diagonal and cross-peaks. (a), (b), and (c) panels correspond to the slope of the low frequency diagonal peak, high frequency diagonal peak, and the right lower corner cross-peak, respectively. The filled squares are the experimental data points and the solid red line is the fit to a single exponential function.

Image of FIG. 9.
FIG. 9.

Theoretical FFCF and FFXCF of the oxalate ion of the asymmetric stretch vibrational modes. The top and bottom panels correspond to the frequency–frequency autocorrelation and cross-correlation functions, respectively. Panels (a) and (b) correspond to the auto- and cross-correlation, respectively. The red lines correspond to the fitting with a sum of exponential functions (see text).

Image of FIG. 10.
FIG. 10.

Time dependence of the population probabilities, P. Open squares and black lines represent the time evolution of the site populations with the single site as an initial condition. Filled triangles and red lines show the time dependence of the site populations for the eigenstate coefficient derived from the time averaged Hamiltonian.

Image of FIG. 11.
FIG. 11.

Theoretical and experimental FTIR spectra of C13-oxalate ion in DO. The open circles (bottom axis) represent the experimental data points, whereas the solid black, dashed red, and dotted blue lines (top axis) represent the total FTIR and the and components predicted by the theory, respectively.

Tables

Generic image for table
Table I.

Parameters of the population and anisotropy dynamics fit for the different parts of the transient spectrum.

Generic image for table
Table II.

Parameters of the experimental frequency auto- and cross-correlation functions.

Generic image for table
Table III.

Parameters of the theoretically predicted frequency auto- and cross-correlation functions.

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/content/aip/journal/jcp/139/16/10.1063/1.4826137
2013-10-30
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibrational dynamics of a non-degenerate ultrafast rotor: The (C12,C13)-oxalate ion
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/16/10.1063/1.4826137
10.1063/1.4826137
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