title: An extrapolation method for the efficient calculation of molecular response properties within Born-Oppenheimer molecular dynamics.
abstract: The calculation of molecular response properties in dynamic molecular systems is a major challenge that requires sampling over many steps of, e.g., Born-Oppenheimer molecular dynamics (BO-MD) simulations. We present an extrapolation scheme to accelerate such calculations for multiple steps within BO-MD trajectories or equivalently within other sampling methods of conformational space. The extrapolation scheme is related to the one introduced by Pulay and Fogarasi [Chem. Phys. Lett., 2004, 386, 272] for self-consistent field (SCF) energy calculations. We extend the extrapolation to the quantities within our density matrix-based Laplace-transformed coupled perturbed SCF (DL-CPSCF) method that allows for linear-scaling calculations of response properties for large molecular systems. Here, we focus on the example of calculating NMR chemical shifts for which the number of required DL-CPSCF iterations reduces by roughly 40-70%.
authors.affiliation: Chair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Munich, Germany.
authors.forename: Denis
authors.initials: D
authors.lastname: Flaig
authors.forename: Christian
authors.initials: C
authors.lastname: Ochsenfeld
mesh_terms: D000465:Algorithms; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D056004:Molecular Dynamics Simulation; D009930:Organic Chemicals / Q000737:chemistry
chemical_list: D009930:Organic Chemicals