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arxiv: physics/0012012 · v1 · submitted 2000-12-06 · ⚛️ physics.chem-ph · quant-ph

Perturbative treatment of intercenter coupling in Redfield theory

classification ⚛️ physics.chem-ph quant-ph
keywords couplingintercentertreatmentartifactscoupledevenperturbativeaddition
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The quantum dynamics of coupled subsystems connected to a thermal bath is studied. In some of the earlier work the effect of intercenter coupling on the dissipative part was neglected. This is equivalent to a zeroth-order perturbative expansion of the damping term with respect to the intercenter coupling. It is shown numerically for two coupled harmonic oscillators that this treatment can lead to artifacts and a completely wrong description, for example, of a charge transfer processes even for very weak intercenter coupling. Here we perform a first-order treatment and show that these artifacts disappear. In addition, we demonstrate that the thermodynamic equilibrium population is almost reached even for strong intercenter coupling strength.

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