Journal of Chemical Physics, Vol.115, No.22, 10291-10302, 2001
Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. II. Generalizations based on mass-weighting, idempotency, energy conservation and choice of initial conditions
A generalization is presented here for a newly developed approach to ab initio molecular dynamics, where the density matrix is propagated with Gaussian orbitals. Including a tensorial fictitious mass facilitates the use of larger time steps for the dynamics process. A rigorous analysis of energy conservation is presented and used to control the deviation of the fictitious dynamics trajectory from the corresponding Born-Oppenheimer dynamics trajectory. These generalizations are tested for the case of the Cl-(H2O)(25) cluster. It is found that, even with hydrogen atoms present in the system, no thermostats are necessary to control the exchange of energy between the nuclear and the fictitious electronic degrees of freedom.