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CarParrinello methodThe CarParrinello method in computational chemistry is a type of ab initio (first principles) molecular dynamics, usually employing periodic boundary conditions, planewave basis sets, and DFT. In contrast to BornOppenheimer molecular dynamics wherein the nuclear (ions) degree of freedom are propagated using ionic forces which are calculated at each iteration by approximately solving the electronic problem with conventional matrix diagonalization methods, the CarParrinello method explicitly introduces the electronic degrees of freedom as (fictitious) dynamical variables, writing an extended Lagrangian for the system which leads to a system of coupled equations of motion for both ions and electrons. In this way an explicit electronic minimization at each iteration is not needed: after an initial standard electronic minimization, the fictitious dynamics of the electrons keep them on the electronic ground state corresponding to each new ionic configuration visited along the dynamics, thus yielding accurate ionic forces. In order to maintain this adiabaticity condition, it is necessary that the fictitious mass of the electrons is chosen small enough to avoid a significant energy transfer from the ionic to the electronic degrees of freedom. This small fictitious mass in turn requires that the equations of motion are integrated using a smaller time step than the ones (110 fs) commonly used in BornOppenheimer molecular dynamics. Additional recommended knowledge
Fictitious DynamicsLagrangianWhere is the KohnSham energy density functional, which outputs energy values when given KohnSham wavefunctions and nuclear positions. Orthogonality Constraintwhere δ_{ij} is the Kronecker Delta function. Equations of MotionYou get the Equations of Motion by taking the stationary point of the Lagrangian with respect to ψ_{i} and R_{I}, with the orthogonality constraint. BornOppenheimer LimitIn the formal limit where , the Equations of Motion approach BornOppenheimer Molecular Dynamics. However numerical implementation limit can lead to inefficient rapid oscillatory trajectories; given the integration framework and according to the problem, μ has to be chosen judiciously. References
See alsoCarParrinello Molecular Dynamics, a software package implementing the method. Categories: Molecular dynamics  Quantum chemistry 

This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "CarParrinello_method". A list of authors is available in Wikipedia. 