Analytic gradients for spin multiplets in natural orbital functional theory.

Abstract

Analytic energy gradients with respect to nuclear motion are derived for non-singlet compounds in the natural orbital functional theory. We exploit the formulation for multiplets in order to obtain a simple formula valid for any many-electron system in its ground mixed state with a total spin S and all possible spin projection Sz values. We demonstrate that the analytic gradients can be obtained without resorting to linear response theory or involving iterative procedures. A single evaluation is required, so integral derivatives can be computed on-the-fly along the calculation, thus improving the effectiveness of screening by the Schwarz inequality. The results for small- and medium-sized molecules with many spin multiplicities are shown. Our results are compared with the experimental data and accurate theoretical equilibrium geometries.