In this work we formulate an ab-initio perturbative theory for the dynamics of a many electron state, dressed by the presence of the finite-temperature polaron bath. The Lang-Firsov canonical transformation is used to convert the usual many-electron theory into a theory of many polarons (electrons coupled to a possibly infinite bosonic bath). A dynamical model correct to second-order in electron-electron correlation and electron-boson coupling simultaneously  is presented. The model's cost scales with the 5th order of single electron basis and linearly with the dynamical structure of the bath. It can be used to simulate absorbtion lineshapes beyond the Markov approximation, and excitonic transport physics.When the vibrations of a molecule are incorporated into the polaron model as bosons, they provide a dynamics beyond the Born-Oppenheimer approximation, uniquely defined by only a Hessian and orbital gradient calculation. Quantities central to energy conversion and transport like the real-space size of moving electrons (excitations, holes etc.), and transfer rates as a function of bath strength can be calculated from first-principles using the formalism. Exciton charge-separation is an intrinsically many-body, dissipative application of special interest. The model is a high-accuracy (high-cost) standard to which more affordable density-coupling methods based on purely electronic excited states may be compared. Resonant response properties, which do not diverge, are also given by the formalism without phenomenological parameters. Example propagations with a developmental code are given. Relationships with other second-order theories of electronic dynamics are explored, and possible extensions beyond perturbation theory.

Polaron transformed electonic response theory

244th National Meeting (2012)

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