Chemical hardness, linear response, and pseudopotential transferability

We propose a systematic method of analyzing pseudopotential transferability based on linear-response properties of the free atom, including self-consistent chemical hardness and polarizability. Our calculation of hardness extends the approach of Teter not only by including self-consistency, but also by generalizing to nondiagonal hardness matrices, thereby allowing us to test for transferability to nonspherically symmetric environments. We apply the method to study the transferability of norm-conserving pseudopotentials for a variety of elements in the Periodic Table. We find that the self-consistent corrections are frequently significant, and should not be neglected. We prove that the partial-core correction improves the pseudopotential hardness of alkaline metals considerably. We propose a quantity to represent the average hardness error and calculate this quantity for many representative elements as a function of pseudopotential cutoff radii. We find that the atomic polarizabilities are usually well reproduced by the norm-conserving pseudopotentials. Our results provide useful guidelines for making optimal choices in the pseudopotential generation procedure. © 1995 The American Physical Society.