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A novel method to calculate mode Grüneisen parameters of a material from first principles is presented. This method overcomes the difficulties and limitations of existing approaches, based on the calculation of either third-order force constants or phonon frequencies at different volumes. Our method requires the calculation of phonon frequencies of a material at only the volume of interest, it is based on the second-order differentiation of a corrected stress tensor with respect to normal mode coordinates, and it yields simultaneously all the components of the mode Grüneisen parameters tensor. In this work, after discussing conceptual and technical aspects, the method is applied to silicon, aluminum, scandium fluoride, and a metallic alloy. These calculations show that our method is straightforward and it is suited to be applied to the broad class of materials prone to exhibit structural instabilities, or presenting anisotropy, or chemical and/or structural disorder.

A general method is presented to calculate from first principles the full set of third-order elastic constants of a material of arbitrary symmetry. The method here illustrated relies on a plane-wave density functional theory scheme to calculate the Cauchy stress and the numerical differentiation of the second Piola-Kirchhoff stress tensor to evaluate the elastic constants. It is shown that finite difference formulas lead to a cancellation of the finite basis set errors, whereas simple solutions are proposed to eliminate numerical errors arising from the use of Fourier interpolation techniques. Applications to diamond, silicon, aluminum, magnesium, graphene, and a graphane conformer give results in excellent agreement with both experiments and previous calculations based on fitting energy density curves, demonstrating both the accuracy and generality of our new methodology to investigate nonlinear elastic behaviors of materials.