Theoretical Prediction of Thermal Polarization
P Wirnsberger and C Dellago and D Frenkel and A Reinhardt, PHYSICAL REVIEW LETTERS, 120, 226001 (2018).
DOI: 10.1103/PhysRevLett.120.226001
We present a mean-field theory to explain the thermo-orientation effect in an off-center Stockmayer fluid. This effect is the underlying cause of thermally induced polarization and thermally induced monopoles, which have recently been predicted theoretically. Unlike previous theories that are based either on phenomenological equations or on scaling arguments, our approach does not require any fitting parameters. Given an equation of state and assuming local equilibrium, we construct an effective Hamiltonian for the computation of local Boltzmann averages. This simple theoretical treatment predicts molecular orientations that are in very good agreement with simulation results for the range of dipole strengths investigated. By decomposing the overall alignment into contributions from the temperature and density gradients, we shed further light on how the nonequilibrium result arises from the competition between the two gradients.
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