Non-Born-Oppenheimer molecular dynamics.

Next generation extended Lagrangian first principles molecular dynamics.

Extended Lagrangian Born-Oppenheimer molecular dynamics [A. M. N. Niklasson, Phys. Rev. Lett. 100, 123004 (2008)] is formulated for general Hohenberg-Kohn density-functional theory and compared with the extended Lagrangian framework of first principles molecular dynamics by Car and Parrinello [Phys. Rev. Lett. 55, 2471 (1985)]. It is shown how extended Lagrangian Born-Oppenheimer molecular dyna...

Analysis of Time Reversible Born-Oppenheimer Molecular Dynamics

We analyze the time reversible Born-Oppenheimer molecular dynamics (TRBOMD) scheme, which preserves the time reversibility of the Born-Oppenheimer molecular dynamics even with non-convergent self-consistent field iteration. In the linear response regime, we derive the stability condition, as well as the accuracy of TRBOMD for computing physical properties, such as the phonon frequency obtained ...

Non-Born–Oppenheimer Molecular Dynamics for Conical Intersections, Avoided Crossings, and Weak Interactions

How accurate is molecular dynamics?

Born-Oppenheimer dynamics is shown to provide an accurate approximation of time-independent Schrödinger observables for a molecular system with an electron spectral gap, in the limit of large ratio of nuclei and electron masses, without assuming that the nuclei are localized to vanishing domains. The derivation, based on a Hamiltonian system interpretation of the Schrödinger equation and stabil...

The diagonal Born±Oppenheimer correction to molecular dynamical properties

We examine the e€ect of the diagonal Born±Oppenheimer correction on dynamics in two simple systems ± the Hooke's atom in an external harmonic potential and the collinear hydrogen exchange reaction. The transmission probability for the Hooke's atom, calculated within the Born±Oppenheimer approximation, is simply shifted in energy with respect to the exact result, and this is corrected by the dia...