Density-matrix based Extended Lagrangian Born-Oppenheimer Molecular Dynamics

Abstract: Extended Lagrangian Born-Oppenheimer molecular dynamics [{\em Phys.\ Rev.\ Lett.\ } {\bf 2008}, {\em 100}, 123004] is presented for Hartree-Fock theory, where the extended electronic degrees of freedom are represented by a density matrix, including fractional occupation numbers at elevated electronic temperatures. In contrast to regular direct Born-Oppenheimer molecular dynamics simulations, no iterative self-consistent field optimization is required prior to the force evaluations. To sample regions of the potential energy landscape where the gap is small or vanishing, which leads to particular convergence problems in regular direct Born-Oppenheimer molecular dynamics simulations, an adaptive integration scheme for the extended electronic degrees of freedom is presented. The integration scheme is based on a tunable, low-rank approximation of a fourth-order kernel, ${\cal K}$, that determines the metric tensor, ${\cal T}\equiv {\cal K}^T{\cal K}$, used in the extended harmonic oscillator of the Lagrangian that generates the dynamics of the electronic degrees of freedom. The formulation and algorithms provide a general guide to implement extended Lagrangian Born-Oppenheimer molecular dynamics for quantum chemistry, density functional theory, and semiempirical methods using a density matrix formalism.