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Orientational Pair Correlations in a Dipolar Molecular Liquid: Time-Resolved Resonant and Nonresonant Pump–Probe Spectroscopies
journal contribution
posted on 2018-11-09, 00:00 authored by Steven
A. Yamada, Heather E. Bailey, Michael D. FayerOrientational pair
correlations (OPCs), when they are sufficiently
strong in a liquid, contain information on the interplay between structure
and dynamics that arise from intermolecular interactions. Consequently,
the quantification of OPCs remains a subject of substantial interest
in current experimental and theoretical works. In the case of benzonitrile,
the importance of OPCs remains ambiguous, owing to the use of model-dependent
analyses or reliance on a single spectroscopic technique. Here, IR
polarization-selective pump–probe (PSPP) and optical heterodyne-detected
optical Kerr effect (OHD-OKE) experiments were used to quantify OPCs
in benzonitrile. These methods measure single molecule and collective
orientational relaxation dynamics, respectively. A comparison of the
orientational correlation function (PSPP) of the naturally abundant 13CN stretching mode and the polarizability anisotropy relaxation
(OHD-OKE) of the liquid revealed that the collective reorientation
time was a factor of 1.56 ± 0.08 slower than the single molecule
reorientation time. The two types of measurements on dilute benzonitrile
in carbon tetrachloride were the same within experimental error. These
results support the proposition that OPCs exist and arise from the
formation of parallel-aligned intermolecular structures in the neat
liquid.
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Keywords
IR polarization-selectivebenzonitrileorientational correlation functionOrientational Pair Correlationsmodel-dependent analysesspectroscopic techniquecarbon tetrachloridemethods measureOPCPSPPresults supportKerr effectpolarizability anisotropy relaxationmolecule reorientation timeOHD-OKEreorientation timeorientational relaxation dynamicsTime-Resolved Resonant13 CNDipolar Molecular Liquid
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