Geometry optimization of periodic systems using internal coordinates

摘要

An algorithm is proposed for the structural optimization of periodic systems in internal (chemical) coordinates. Internal coordinates may include in addition to the usual bond lengths, bond angles, out-of-plane and dihedral angles, various "lattice internal coordinates" such as cell edge lengths, cell angles, cell volume, etc. The coordinate transformations between Cartesian (or fractional) and internal coordinates are performed by a generalized Wilson B-matrix, which in contrast to the previous formulation by Kudin [J. Chem. Phys. 114, 2919 (2001)] includes the explicit dependence of the lattice parameters on the positions of all unit cell atoms. The performance of the method, including constrained optimizations, is demonstrated on several examples, such as layered and microporous materials (gibbsite and chabazite) as well as the urea molecular crystal. The calculations used energies and forces from the ab initio density functional theory plane wave method in the projector-augmented wave formalism.