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Watching solvent friction impede ultrafast barrier crossings: A direct test of Kramers theory
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Image of FIG. 1.
FIG. 1.

Pulse sequence and schematic spectra.

Image of FIG. 2.
FIG. 2.

(Top) FT-IR spectra of DCO in hexane with the dashed green peaks assigned to isomer I, dashed blue to isomer II, and dashed orange to isomer III. (Bottom) Cartoon representation of the potential energy surface along the reaction coordinate. The variables are defined in the text.

Image of FIG. 3.
FIG. 3.

(a) Normalized FT-IR spectra of DCO in the series of linear alkane solvents and cyclohexane (CH). (b) Radial distribution functions for isomers I and II (shifted by −0.5) and the transition state (shifted by ) in the series of solvents (same key). The radial distribution functions are of the distances between the center of mass of the solute and the atoms of the solvent.

Image of FIG. 4.
FIG. 4.

The motion of the carbonyl units corresponding to the normal modes is indicated with arrows.

Image of FIG. 5.
FIG. 5.

(a) Absorptive spectra of DCO in hexane at and . (b) Plot of the negative amplitude of peaks 7 (red), 8 (black), 1 (blue), and 6 (green) as a function of .

Image of FIG. 6.
FIG. 6.

Plots of vs (a) and (b) .

Image of FIG. 7.
FIG. 7.

Reduced rate constants with the (a) Kramers-hydrodynamic fit and the (b) Kramers–Hubbard fit.

Image of FIG. 8.
FIG. 8.

(Top) Plots of the reorientation time vs viscosity. The linear alkanes are fit to a line, according to the SED equation. (Bottom) Plot of vs resulting in the isolated solvent dynamics.


Generic image for table
Table I.

The calculated vibrational frequencies and intensities weighted by the scaling factor 0.9725 along with the experimentally determined vibrational frequencies and intensities are given in parentheses.

Generic image for table
Table II.

The extracted forward and reverse rate constants with the corresponding 1/e isomerization time.


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Scitation: Watching solvent friction impede ultrafast barrier crossings: A direct test of Kramers theory