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Title: Density-Matrix Based Extended Lagrangian Born–Oppenheimer Molecular Dynamics

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Extended Lagrangian Born–Oppenheimer molecular dynamics [ Phys. Rev. Lett. 2008, 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, K, that determines the metric tensor, T ≡ KTK, used in the extended harmonic oscillator of the Lagrangian that generates the dynamics of the electronic degrees of freedom. Here, 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.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1843167
Report Number(s):
LA-UR-20-22452
Journal Information:
Journal of Chemical Theory and Computation, Vol. 16, Issue 6; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Mathematics
Born-Oppenheimer molecular dynamics
First principles electronic structure theory
Hartree-Fock
Density matrix
Extended Lagrangian
Molecular dynamics
Algorithms
Optimization
Approximation
Electrical properties