A note on the Pulay force at finite electronic temperatures

摘要

Pulay's original expression for the basis-set dependent adjustment term to the Hellmann-Feynman force in electronic structure theory, which occurs for nonorthogonal local basis-set representations, is based on the idempotency condition of a pure ensemble. At finite electronic temperatures with a fractional occupation of the states, the conventional expression of the Pulay force is therefore no longer valid. Here we derive a simple and computationally efficient expression for a generalized Pulay force, which is suitable for large-scale ab initio simulations at finite electronic temperatures using local nonorthogonal basis-set representations. The generalized Pulay force expression is given in terms of the temperature-dependent density matrix. For the construction of the density matrix, we propose a recursive Fermi operator expansion algorithm that automatically converges to the correct chemical potential.