Accelerating ab initio path integral molecular dynamics with multilevel sampling of potential surface

2014/12/10 by Hua-Yun Geng, Hua Y. Geng · 17 citations
Chemistry · Earth and Planetary Sciences · Mathematics · Physics and Astronomy · #Ab initio #Ab initio quantum chemistry methods #Advanced Chemical Physics Studies #Atomic physics #Chemistry #Extrapolation #High-pressure geophysics and materials #Mathematical analysis #Mathematics #Molecular dynamics #Molecule #Path integral formulation #Physics #Potential energy surface #Quantum mechanics #Quantum, superfluid, helium dynamics #Statistical physics #Thermodynamic integration #cond-mat.stat-mech #physics.chem-ph #physics.comp-ph #quant-ph

paper · pdf · doi:10.1016/j.jcp.2014.12.007

published in Journal of Computational Physics 283, 299-311 (Elsevier BV) · 20 pages, 8 figures

openalex publication_date 2014/12/10 · arxiv created 2014/12/19 · arxiv updated 2014/12/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/06

Abstract

A multilevel approach to sample the potential energy surface in a path integral formalism is proposed. The purpose is to reduce the required number of ab initio evaluations of energy and forces in ab initio path integral molecular dynamics (AI-PIMD) simulation, without compromising the overall accuracy. To validate the method, the internal energy and free energy of an Einstein crystal are calculated and compared with the analytical solutions. As a preliminary application, we assess the performance of the method in a realistic model, the FCC phase of dense atomic hydrogen, in which the calculated result shows that the acceleration rate is about 3 to 4 fold for a two-level implementation, and can be increased to 10 times if extrapolation is used. With only 16 beads used for the ab initio potential sampling, this method gives a well converged internal energy. The residual error in pressure is just about 3 GPa, whereas it is about 20 GPa for a plain AI-PIMD calculation with the same number of beads. The vibrational free energy of the FCC phase of dense hydrogen at 300 K is also calculated with an AI-PIMD thermodynamic integration method, which gives a result of about 0.51 eV/proton at a density of r_s=0.912.

Citations

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• Path integrals in the theory of condensed helium
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Cited by

• Ab initio molecular dynamics with nuclear quantum effects at classical cost: Ring polymer contraction for density functional theory