First-Principles Calculation of Third-Order Elastic Constants via Numerical Differentiation of the Second Piola-Kirchhoff Stress Tensor.

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.