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A mode-coupling theory of vibrational line broadening in near-critical fluids
S A Egorov1, C P Lawrence, J L Skinner
1Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, USA.
Abstract:
We present a fully microscopic mode-coupling theory of near-critical line broadening. All the structural and dynamical input required by the theory is calculated directly from intermolecular potentials. We compute vibrational frequency time-correlation functions and line shapes as the critical point is approached along both the critical isochore and the liquid-gas coexistence curve. Theory is shown to be in good agreement with simulation.
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