Using forces to accelerate first-principles anharmonic vibrational calculations

Abstract

High-level vibrational calculations have been used to investigate anharmonicity in a wide variety of materials using density-functional-theory (DFT) methods. We have developed a new and efficient approach for describing strongly-anharmonic systems using a vibrational self-consistent-field (VSCF) method. By far the most computationally expensive part of the calculations is the mapping of an accurate Born-Oppenheimer (BO) energy surface within the region of interest. Here we present an improved method which reduces the computational cost of the mapping. In this approach we use data from a set of energy calculations for different vibrational distortions of the materials and the corresponding forces on the atoms. Results using both energies and forces are presented for the test cases of the hydrogen molecule, solid hydrogen under high pressure including mapping of two-dimensional subspaces of the BO surface, and the bcc phases of the metals Li and Zr. The use of forces data speeds up the anharmonic calculations by up to 40%.