Higher-Order Extended Lagrangian Born–Oppenheimer Molecular Dynamics for Classical Polarizable Models

• Published in: Journal of chemical theory and computation Vol. 14; no. 2; pp. 499 - 511
• Main Authors: Albaugh, Alex, Head-Gordon, Teresa, Niklasson, Anders M. N
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.02.2018
• Subjects: Computer simulation; Degrees of freedom; Ground state; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Iterative methods; Lagrangian function; Mathematics; Molecular chains; Molecular Dynamics; polarizable force fields; Shadows; Variation; Well construction
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.7b01041

Generalized extended Lagrangian Born–Oppenheimer molecular dynamics (XLBOMD) methods provide a framework for fast iteration-free simulations of models that normally require expensive electronic ground state optimizations prior to the force evaluations at every time step. XLBOMD uses dynamically driven auxiliary degrees of freedom that fluctuate about a variationally optimized ground state of an approximate “shadow” potential which approximates the true reference potential. While the requirements for such shadow potentials are well understood, constructing such potentials in practice has previously been ad hoc, and in this work, we present a systematic development of XLBOMD shadow potentials that match the reference potential to any order. We also introduce a framework for combining friction-like dissipation for the auxiliary degrees of freedom with general-order integration, a combination that was not previously possible. These developments are demonstrated with a simple fluctuating charge model and point induced dipole polarization models.