Abstract
The zeroth and second spectral moments for the far infrared spectral intensity of a polar liquid are analyzed from first principles, taking into account the first-order dipole–induced dipole contribution. The results, based on evaluating the equilibrium averages of appropriate correlation functions, are simplified by considering that the liquid pair distribution function can be approximated by a truncated expansion in terms of Wigner rotation functions. Averages involving three- and four-molecule distribution functions are not considered in the present calculation. The calculated zeroth moment for acetonitrile, M(0)=17.5 D2, compares favorably with the experimental value of 20.7 D2. The difference probably reflects the neglect of three- and four-molecule terms as well as higher order induction effects.
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