Surface excess elasticity of gold: ab initio coefficients and impact on the effective elastic response of nanowires

Abstract

Predicting the influence of the surface on the effective elastic properties of nanoscale structures and nanomaterials remains a challenge, which we here address on both levels, continuum and atomic. Density Functional Theory (DFT) computation at the atomic level yields the first reliable surface excess elastic parameters for the (111) and (001) surfaces of gold. At the continuum level, we derive closed-form expressions for the effective elastic behavior that can be combined with the DFT-derived excess elastic parameters to obtain the effective axial, torsion, and bending stiffness of circular nanowires with surface excess elasticity. The two approaches use different reference frames, and we emphasize the need for consistent stress definitions and for conversion between the separate stress measures when transferring results between the approaches. We present excess elastic parameters separately for Cauchy and 2nd Piola-Kirchhoff stresses, demonstrating that the conversion substantially modifies their numerical value and may even invert their sign. The results afford an assessment of the contribution of the surface excess elastic parameters to the effective elastic response of nanoscale beams or wires. This assessment sheds doubt on earlier suggestions relating experimental observations of an effective stiffening or softening at small size to the excess elasticity of clean surfaces.