Ab Initio Molecular Dynamics on the Electronic Boltzmann Equilibrium Distribution

Abstract

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.

published in New J. Phys

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• Ehrenfest dynamics is purity non-preserving: a necessary ingredient for decoherence
• The generalized quasiharmonic approximation via space group irreducible derivatives
• About the computation of finite temperatureensemble averages of hybrid quantum-classicalsystems with Molecular Dynamics
• Non-adiabatic effects within a single thermally-averaged potential energy surface: Thermal expansion and reaction rates of small molecules
• Identification and Resolution of Unphysical Multielectron Excitations in the Real-Time Time-Dependent Kohn-Sham Formulation