Lagrangian density molecular systems

Car and Parrinello in their celebrated 1985 paper [2] proposed an alternative route for molecular simulations of electrons and nuclei altogether, in the framework of density functional theory. Their idea was to reintroduce the expansion coefficients Cj(G) of the Kohn-Sham orbitals in the plane wave basis set, with respect to which the Kohn-Sham energy functional should be minimized, as degrees of freedom of the system. They then proposed an extended Car-Parrinello Lagrangian for the system, which has dependance on the fictitious degrees of freedom Cj(G) and their time derivative Cj (G) ... 

In order to overcome the limitations of currently available empirical force field param-eterizations, we performed Car-Parrinello (CP) Molecular Dynamic simulations [36]. In the framework of DFT, the Car-Parrinello method is well recognized as a powerful tool to investigate the dynamical behaviour of chemical systems. This method is based on an extended Lagrangian MD scheme, where the potential energy surface is evaluated at the DFT level and both the electronic and nuclear degrees of freedom are propagated as dynamical variables. Moreover, the implementation of such MD scheme with localized basis sets for expanding the electronic wavefunctions has provided the chance to perform effective and reliable simulations of liquid systems with more accurate hybrid density functionals and nonperiodic boundary conditions [37]. Here we present the results of the CPMD/QM/PCM approach for the three nitroxide derivatives sketched above details on computational parameters can be found in specific papers [13]. 

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