Dynamical resonances, Floquet Hamiltonian

The models for the control processes start with the Schrodinger equation for the molecule in interaction with a laser field that is treated either as a classical or as a quantized electromagnetic field. In Section II we describe the Floquet formalism, and we show how it can be used to establish the relation between the semiclassical model and a quantized representation that allows us to describe explicitly the exchange of photons. The molecule in interaction with the photon field is described by a time-independent Floquet Hamiltonian, which is essentially equivalent to the time-dependent semiclassical Hamiltonian. The analysis of the effect of the coupling with the field can thus be done by methods of stationary perturbation theory, instead of the time-dependent one used in the semiclassical description. In Section III we describe an approach to perturbation theory that is based on applying unitary transformations that simplify the problem. The method is an iterative construction of unitary transformations that reduce the size of the coupling terms. This procedure allows us to detect in a simple way dynamical or field induced resonances—that is, resonances that... 

As we have stated, the Floquet Hamiltonian (113) has no terms that are resonant if we take small enough e, and the iteration of the KAM procedure converges. However, if we take e large enough, we encounter new resonances that are not present at zero or small fields that is, they are not related to degeneracies of the unperturbed eigenvalues of Kq that lead to the zero-field resonances we have discussed in the previous subsection. These new resonances are related to degeneracies of the new effective unperturbed operator K 0(e), which appear at some specific finite values of e. These are the dynamical resonances. 

Care must be exercised to distinguish the concept of adiabatic Floquet dynamics introduced here, which refers to an adiabatic time-evolution, or to the slow variations of the Floquet basis with time, from the concept of adiabatic representation defined in the previous section, which refers to the slow variations of the electronic Hamiltonian (Floquet or not) with respect to nuclear motions (i.e., the noncommutativity of the electronic Hamiltonian Hei and the nuclear KE operator Tjv). Where confusion is possible and to be avoided, we shall refer to this concept of adiabaticity related to the BO approximation as the R-adiabaticity, while adiabaticity in actual time evolution will be termed t-adiabaticity. Non-adiabatic effects in time evolution are due to a fast variation of the (Floquet) Hamiltonian with time, causing Floquet states to change rapidly in time, to the extent that in going from one time slice to another, a resonance may be projected onto many new resonances as well as diffusion (continuum) states [40], and the Floquet analysis breaks down completely. We will see in Section 5 how one can take advantage of such effects to image nuclear motions by an ultrafast pump-probe process. 

In this chapter, the main theoretical tools used in the work presented in the next two chapters on the laser control of the radiationless decay in pyrazine and of the tunneling dynamics in NHD2, are introduced. After a brief discussion of the main approximations generally made in the study of laser-molecule interactions, presented in Sect. 6.1, we introduce in Sect. 6.2 the most basic tools for the laser control of population transfer in a two-level system. The derivation of an effective Hamiltonian allowing for the description of the interaction of a molecular system with a strong non-resonant laser pulse is presented in Sect. 6.3. TheFloquet theory and the adiabatic Floquet theory are Anally introduced in Sects. 6.4 and 6.5. 

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