Schrodinger equation 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... 

We will discuss the Floquet approach from two different points of view. In the first one, discussed in Section II.A, the Floquet formalism is just a mathematically convenient tool that allows us to transform the Schrodinger equation with a time-dependent Hamiltonian into an equivalent equation with a time-independent Hamiltonian. This new equation is defined on an enlarged Hilbert space. The time dependence has been substituted by the introduction of one auxiliary dynamical variable for each laser frequency. The second point of... 

The Schrodinger equation of the Floquet Hamiltonian in JT, where 9 is a dynamical variable, is equivalent, in an interaction representation, to the semiclassical Schrodinger equation in where 0 is considered as a parameter corresponding to the fixed initial phase. The dynamics of the two models are identical if the initial photon state in the Floquet model is a coherent state. 

Interaction Representation The Schrodinger equation of the Floquet Hamiltonian in... 

The Born-Oppenheimer approximation allows us to decouple the electronic and nuclear motions of the free molecule of the Hamiltonian Hq. Solving the Schrodinger equation //o l = with respect to the electron coordinates r = r[, O, gives rise to the electronic states (r, R) = (r n(R)), n = 0,..., Ne, of respective energies En (R) as functions of the nuclear coordinates R, with the electronic scalar product defined as (n(R) n (R))r = j dr rj( r. R) T,-(r, R). We assume Ne bound electronic states. The Floquet Hamiltonian of the molecule perturbed by a field (of frequency co, of amplitude 8, and of linear polarization e), in the dipole coupling approximation, and in a coordinate system of origin at the center of mass of the molecule can be written as... 

We first derive the time-dependent dressed Schrodinger equation generated by the Floquet Hamiltonian, relevant for processes induced by chirped laser pulses (see Section IV.A). The adiabatic principles to solve this equation are next described in Section IV.B. 

The preceding analysis is well adapted when one considers slowly varying laser parameters. One can study the dressed Schrodinger equation invoking adiabatic principles by analyzing the Floquet Hamiltonian as a function of the slow parameters. 

In this Appendix we sketch an argument that leads to the adiabatic theorem for an A-level system with a Floquet Hamiltonian denoted Kr which generates the dressed Schrodinger equation [Eq. (229) of Section IV],... 

The RWA is appropriate when the Rabi frequency is much smaller than the other frequencies in the problem, viz. the transition frequency and the detuning. The first of these conditions limits the intensity, and so ultimately RWA breaks down it then becomes necessary to include the effects of the counterrotating terms, and one returns to solving the time-dependent Schrodinger equation, with a Hamiltonian which is periodic in time this is done in a more general way by applying Floquet s theorem for differential equations with periodically varying coefficients. 

Presumably the most straightforward approach to chemical dynamics in intense laser fields is to use the time-independent or time-dependent adiabatic states [352], which are the eigenstates of field-free or field-dependent Hamiltonian at given time points respectively, and solve the Schrodinger equation in a stepwise manner. However, when the laser field is approximately periodic, one can also use a set of field-dressed periodic states as an expansion basis. The set of quasi-static states in a periodic Hamiltonian is derived by a Floquet type analysis and is often referred to as the Floquet states [370]. Provided that the laser field is approximately periodic, advantages of using the latter basis set include (1) analysis and interpretation of the electron dynamics is clearer since the Floquet state population often vary slowly with the timescale of the pulse envelope and each Floquet state is characterized as a field-dressed quasi-stationary state, (2) under some moderate conditions, the nuclear dynamics can be approximated by mixed quantum-classical (MQC) nonadiabatic dynamics on the field-dressed PES. The latter point not only provides a powerful clue for interpretation of nuclear dynamics but also implies possible MQC formulation of intense field molecular dynamics. 

The Floquet theorem, when apphed to the quantum mechanics [370], implies the stationarity of Floquet states imder a perfectly periodic Hamiltonian. We define the electronic Floquet operator as 7ft = Hf — ihdt and the Floquet states as its periodic eigenstates which satisfy Tlt x t)) = A] A(f))- The above mentioned stationarity states that the solution of time-dependent Schrodinger equation ] t) can be expanded as... 

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