Density functional theory method for twisted geometries with application to torsional deformations in group-IV nanotubes

Abstract

We present a real-space formulation and implementation of Kohn-Sham Density Functional Theory suited to twisted geometries, and apply it to the study of torsional deformations of X (X = C, Si, Ge, Sn) nanotubes. Our formulation is based on higher order finite difference discretization in helical coordinates, uses ab initio pseudopotentials, and naturally incorporates rotational (cyclic) and screw operation (i.e., helical) symmetries. We discuss several aspects of the computational method, including the form of the governing equations, d ils of the numerical implementation, as well as its convergence, accuracy and efficiency properties.The technique presented here is particularly well suited to the first principles simulation of quasi-one-dimensional structures and their deformations, and many systems of interest can be investigated using small simulation cells containing just a few atoms. We apply the method to systematically study the properties of single-wall zigzag and armchair group-IV nanotubes in the range of (approximately) 1 to 3 nm radius, as they undergo twisting. For the range of deformations considered, the mechanical behavior of the tubes is found to be largely consistent with isotropic linear elasticity, with the torsional stiffness, ktwist, varying as the cube of the nanotube radius. Furthermore, for a given tube radius, ktwist is seen to be highest for carbon nanotubes and the lowest for those of tin, while nanotubes of silicon and germanium are found to have intermediate values of this quantity close to each other. We also describe different aspects of the variation in electronic properties of the nanotubes as they are twisted. In particular, we find that akin to the well known behavior of armchair carbon nanotubes, armchair nanotubes of silicon, germanium and tin also exhibit bandgaps that vary periodically with imposed rate of twist, and that the periodicity of the variation scales in an inverse quadratic manner with the tube radius. These examples highlight the utility of the proposed method in the accurate and efficient computational characterization of important nanomaterials from first principles.