Is depolarized light scattered from simple liquids mainly double-scattered?
✍ Scribed by T. Keyes; Branka M. Ladanyi; Paul A. Madden
- Publisher
- Elsevier Science
- Year
- 1979
- Tongue
- English
- Weight
- 520 KB
- Volume
- 64
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
The multiple-scattering series for depohrized light scattering from simple liquids is investigated. It is found that the leading term in the serif%, due to doubIe-double scattering, is probably not large compared to double-triple (DT) scattering contributions_ Existing theories, which neglect DT scattering, have concluded that the experimental data cannot be explained using the dipole-induced dipole (DID) model for the pair polarizability. It is suggested that p theory nhich includes DT scatterins will not lead to rejection of the DID model. I _ Introduction The earliest theories [l] of the depolarized light scattering intensity (Z) for fluids composed of spherical particies were based upon the dipole-induced dipole (DID) model and upon the assumption that only the two-body ("double scattering") term in the interaction-induced polarizability is important, that is Z=ZDo whereZDO is the* double-double depolarized intensity_ A quantitative test of this theory against experiment [2] requires an accurate two-body potential for the low-density gas or the two-, three-and four-body distnbution functions for the liquid-The most recent experimental work on the gas phase [3,4] indicates that the model predicts reasonably well (up to 20% difference) the integrated intensity and that earlier studies had contradicted this result because they had underestimated the experimental intensity at very low frequency_ Alder et al. [S] have calculated ZDD for hard-sphere and Lennard-Jones fluids representative of argon. They found that the calculated intensity was an order of magnitude greater than the experimental value [6] at the triple-point density and temperature, and attributed this disagreement to failure of the DID model for the pair polarizability-Many quantum-mechanical calculations [7] of the pair polarizability have been performed_ Most show a substantial reduction in the anisotropy below the DID value at physically important separations. However. some of the 'ab initio studies can be criticised on the grounds of basis-set superposition errors [Sj and neglect of correlation. Dacre [9] performed a very accurate calculation on He2 in which both these effects are included; the deviations he finds from DID are not large at the important separations_ Clarke et al. [IO] made a critical study of the semianalytical extensions of the DID model and have shown how many of the corrections to DID expected at short range cancel for the inert gases so that the departures from DID are small [ 111, that is, consistent with the 20% disagreement between theory and experiment in the gas phase but not with the factor of 10 indicated by the comparison in the liquid_ With the exception of the comparisorL of the calculated and experimental liquid-state intensity, the above survey indicates that the DID model of the pair polarizability anisotropy is an excellent first approximation. It is our goal to explain the liquid-state experiments within the DID modeI; this note represents our first step towards this goal.
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