Thermal Expansion from Stochastic Nonlinear Acoustic Fields
The methods of stochastic mechanics are applied to nonlinear acoustic fields generated by random acoustic radiation sources associated with oscillating lattice sites in nonlinear lattices. The assumption of stochastically independent zero-point and temperature-dependent acoustic fields leads to expressions of the thermodynamic internal and Helmholtz free energies per unit mass in terms of modal energies per unit mass that account for the nonlinearity of the propagation modes. The thermodynamic state functions canonically transform to the familiar results of a system of quantized, simple harmonic oscillators in the linear field limit. The thermal expansion coefficient, derived from the Helmholtz free energy per unit mass, is obtained as a sum of the zero-point modal nonlinearity parameters, weighted by temperature-dependent, modal heat capacities. The relationship is fully anharmonic, in contrast to commonly used quasi-harmonic models, and predicts with excellent agreement the experimentally observed null thermal expansion of vitreous silica at the ‘cross-over’ temperature corresponding to the balance between long wavelength modes that contribute negative nonlinearity parameters to the modal sum and short wavelength modes that contribute positive nonlinearity parameters.