Theoretical prediction of thermal polarisation

TL;DR

This paper develops a mean-field theoretical framework to predict thermo-orientation and thermally induced polarisation in off-centre Stockmayer fluids, aligning well with simulations without fitting parameters.

Contribution

It introduces a parameter-free mean-field theory for thermo-orientation, linking local thermodynamic properties to molecular alignment in non-equilibrium conditions.

Findings

Predicted molecular orientations match simulation data.

Decomposition reveals the roles of temperature and density gradients.

The theory explains the origin of thermally induced polarisation.

Abstract

We present a mean-field theory to explain the thermo-orientation effect in an off-centre Stockmayer fluid. This effect is the underlying cause of thermally induced polarisation 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 non-equilibrium result arises from the competition between the two gradients.