Communication: Linear-expansion shooting techniques for accelerating self-consistent field convergence

Abstract

Based on the corrected Hohenberg-Kohn-Sham total energy density functional [Y. A. Zhang and Y. A. Wang, J. Chem. Phys. 130, 144116 (2009)], we have developed two linear-expansion shooting techniques (LIST)– direct LIST (LISTd) and indirect LIST (LISTi), to accelerate the convergence of self-consistent field (SCF) calculations. Case studies show that overall LISTi is the most robust and efficient algorithm for accelerating SCF convergence, whereas LISTd is advantageous in the early stage of an SCF process. More importantly, LISTi outperforms Pulay’s direct inversion in the iterative subspace (DIIS) [P. Pulay, J. Comput. Chem. 3, 556 (1982)] and its two recent improvements, energy-DIIS [K. N. Kudin, G. E. Scuseria, and E. Cancès, J. Chem. Phys. 116, 8255 (2002)] and augmented Roothaan-Hall energy-DIIS [X. Hu and W. Yang, J. Chem. Phys. 132, 054109 (2010)].