THE OPTICAL KERR EFFECT OF LIQUIDS
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Optical Kerr effect (OKE) spectroscopy has found broad use in monitoring ultrafast dynamics in transparent media. I demonstrated that by using two pump pulses with independently-controllable polarizations, intensity and timing, different contributions to the OKE signal in liquids can be enhanced and suppressed, and I characterize in detail perpendicularly-polarized pulses used for the excitation step in OKE spectroscopy. The results indicate that the signal can be described well as arising from the sum of independent third-order responses initiated by each pump pulse.
OKE spectroscopy has been used to study the orientational dynamics of benzene and benzene-d6 confined in nanoporous sol-gel glass monoliths with a range of average pore sizes. The orientational dynamics are described well by the sum of two exponentials, one of which depends on pore size. Comparision to Raman linewidth data suggests that the liquid exhibits significant structuring at the pore walls, with the benzene molecules lying flat on the surfaces of unmodified pores. OKE spectroscopy has also been used to study the temperature-dependent orientational dynamics of a series of nitriles with n-alkyl chains ranging from one to 11 carbons in length. In all cases the orientational diffusion is found to be described by a single-exponential decay. Analysis of the orientational correlation times using the Debye-Stokes-Einstein equation suggests that the molecules adopt extended configurations and reorient as rigid rods. The liquids with shorter alkyl chains undergo an apparent ordering transition as they are cooled.