• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1102-1106
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• 2003

In our previous work we developed the Finite Field method in order to calculate the fifth-order Raman response. The method was applied to calculate various polarization components of the two-dimensional response of liquid $CS_2$. So far, all calculations relied on the dipole-induced dipole. Accurate time-dependent density functional theory calculations have shown that this model has big discrepancies, when molecules are close together as in the liquid. We now report results of investigations on the importance of multipole and electron overlap effects on the polarizability and the fifth-order Raman response. It is shown that these collision effects, especially the induced multipoles, are crucial in the description of the fifth-order response. The impact is found to be especially pronounced for the χ_{mmzzzz}^{(5)}$response that is solely due to interaction induced effects. The calculated response will be compared with various experimental results.