First principles molecular dynamics without self-consistent field optimization

Abstract

We present a first principles molecular dynamics approach that is based on time-reversible ex- tended Lagrangian Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 100, 123004 (2008)] in the limit of vanishing self-consistent field optimization. The optimization-free dynamics keeps the computational cost to a minimum and typically provides molecular trajectories that closely follow the exact Born-Oppenheimer potential energy surface. Only one single diagonalization and Hamiltonian (or Fockian) costruction are required in each integration time step. The proposed dy- namics is derived for a general free-energy potential surface valid at finite electronic temperatures within hybrid density functional theory. Even in the event of irregular functional behavior that may cause a dynamical instability, the optimization-free limit represents an ideal starting guess for force calculations that may require a more elaborate iterative electronic ground state optimization. Our optimization-free dynamics thus represents a flexible theoretical framework for a broad and general class of ab initio molecular dynamics simulations.

11 pages, 7 figures

References in corpus (3)

• An Efficient and Accurate Car-Parrinello-like Approach to Born-Oppenheimer Molecular Dynamics
• Time-reversible Born-Oppenheimer molecular dynamics
• Efficient formalism for large scale ab initio molecular dynamics based on time-dependent density functional theory

Cited by in corpus (7)

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• Graph-based linear scaling electronic structure theory
• Next generation extended Lagrangian first principles molecular dynamics
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• Shadow molecular dynamics and atomic cluster expansions for flexible charge models
• Shadow Energy Functionals and Potentials in Born-Oppenheimer Molecular Dynamics
• Graph-based Quantum Response Theory and Shadow Born-Oppenheimer Molecular Dynamics