Ab Initio Molecular Dynamics on the Electronic Boltzmann Equilibrium Distribution

New Journal Of Physics 12, 083064 (2010)

Ab Initio Molecular Dynamics on the Electronic Boltzmann Equilibrium Distribution

J.L. Alonso, A. Castro, P. Echenique, V. Polo, A. Rubio, D. Zueco

We prove that for a combined system of classical and quantum particles, it is possible to write a dynamics for the classical particles that incorporates in a natural way the Boltzmann equilibrium population for the quantum subsystem. In addition, these molecular dynamics do not need to assume that the electrons immediately follow the nuclear motion (in contrast to any adiabatic approach), and do not present problems in the presence of crossing points between different potential energy surfaces (conical intersections or spin-crossings). A practical application of this molecular dynamics to study the effect of temperature in molecular systems presenting (nearly) degenerate states – such as the avoided crossing in the ring-closure process of ozone – is presented.

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Doi
http://dx.doi.org/10.1088/1367-2630/12/8/083064
arxiv
http://arxiv.org/abs/1002.4899
More Information
http://iopscience.iop.org/1367-2630/12/8/083064/

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