Fifth-order Raman spectroscopy of liquid benzene
| Autor: | L. Huang, R. J. D. Miller, Y. L. Li, Christopher J. Milne, Thomas L. C. Jansen |
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| Přispěvatelé: | Theory of Condensed Matter |
| Jazyk: | angličtina |
| Rok vydání: | 2006 |
| Předmět: |
Phase (waves)
Analytical chemistry NONLINEAR SPECTROSCOPY Molecular physics Signal symbols.namesake NONRESONANT INTERMOLECULAR SPECTROSCOPY Correlation function Materials Chemistry Coherent anti-Stokes Raman spectroscopy Physical and Theoretical Chemistry Spectroscopy HETERODYNE-DETECTION Chemistry ATOMIC LIQUID Anharmonicity Intermolecular force FEMTOSECOND 2-DIMENSIONAL SPECTROSCOPY NORMAL-MODE THEORY MOLECULAR-DYNAMICS SIMULATION Surfaces Coatings and Films DETERMINISTIC PROTEIN MOTIONS DIFFRACTIVE OPTICS symbols Raman spectroscopy PLACZEK APPROXIMATION |
| Zdroj: | Journal of Physical Chemistry B, 110(40), 19867-19876. AMER CHEMICAL SOC |
| ISSN: | 1520-5207 1520-6106 1089-5647 |
| DOI: | 10.1021/jp062063v |
| Popis: | The heterodyned fifth-order Raman response of liquid benzene has been measured and characterized by exploiting the passive-phase stabilization of diffractive optics. This result builds on our previous work with liquid carbon disulfide and extends the spectroscopy to a new liquid for the first time. The all-parallel and Dutch Cross polarization tensor elements are presented for both the experimental results and a finite-field molecular dynamics simulation. The overall response characteristics are similar to those of liquid carbon disulfide: a complete lack of signal along the pump delay, an elongated signal along the probe delay, and a short-lived signal along the time diagonal. Of particular interest is the change in phase between the nuclear and electronic response along the probe delay and diagonal which is not seen in CS(2). Good agreement is achieved between the experiment and the finite-field molecular dynamics simulation. The measurement of the low-frequency Raman two-time delay correlation function indicates the intermolecular modes of liquid benzene to be primarily homogeneously broadened and that the liquid loses its nuclear rephasing ability within 300 fs. This rapid loss of nuclear correlations indicates a lack of modal character in the low-frequency motions of liquid benzene. This result is a validation of the general nature of the technique and represents an important step forward with respect to the use of nonlinear spectroscopy to directly access information on the anharmonic motions of liquids. |
| Databáze: | OpenAIRE |
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