A mode-coupling theory of vibrational line broadening in near-critical fluids.
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.
Egorov
S A
SA
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, USA.
Lawrence
C P
CP
Skinner
J L
JL