Wavepacket control

T. Kobayashi I would like to make the comment that an interesting application of wavepacket control [1] is phonon squeezing in molecular systems and the creation of the Schrodinger cat state. It was theoretically predicted that there are several mechanisms that lead to squeezing of phonon states. 

The research areas treated in this series will be (i) atoms, molecules, and clusters in intense laser fields, (ii) control of molecules and clusters in intense laser fields, (iii) attosecond pulse generation, metrology, and applications, (iv) wavepacket control for high-order harmonics, (v) generation,... 

An additional result that emerges from our study concerns the extent to which wavepacket control is possible using coherent pulse sequences. In a two-level system one can exchange the phases of the two levels with a 7t pulse and, in effect, achieve time reversal of the state of the system. In a multilevel system the extent of control is much more restricted. The center of the wavepacket evolves according to the Franck-Condon principle and Hamilton s equations of motion, which in turn are dictated by nature s potential energy surfaces. What can be controlled by the experimenter is the instant at which the wavepacket changes surfaces. This concept forms the basis for a scheme for controlling the selectivity of a reaction,24,25 which we discuss in the next section. 

A different theory of local control has been derived from the viewpoint of global optimization, applied to finite time intervals [58-60]. This approach can also be applied within a classical context, and local control fields from classical dynamics have been used in quantum problems [61]. In parallel, Rabitz and coworkers developed a method termed tracking control, in which Ehrenfest s equations [26] for an observable is used to derive an explicit expression for the electric field that forces the system dynamics to reproduce a predefined temporal evolution of the control observable [62, 63]. In its original form, however, this method can lead to singularities in the fields, a problem circumvented by several extensions to this basic idea [64-68]. Within the context of ground-state vibration, a procedure similar to tracking control has been proposed in Ref. 69. In addition to the examples already mentioned, the different local control schemes have found many applications in molecular physics, like population control [55], wavepacket control [53, 54, 56], control within a dissipative environment [59, 70], and selective vibrational excitation or dissociation [64, 71]. Further examples include isomerization control [58, 60, 72], control of predissociation [73], or enantiomer control [74, 75]. 

This section begins with a brief description of the basic light-molecule interaction. As already indicated, coherent light pulses excite coherent superpositions of molecular eigenstates, known as wavepackets , and we will give a description of their motion, their coherence properties, and their interplay with the light. Then we will turn to linear and nonlinear spectroscopy, and, finally, to a brief account of coherent control of molecular motion. 

The pioneering use of wavepackets for describing absorption, photodissociation and resonance Raman spectra is due to Heller [12, 13,14,15 and 16]- The application to pulsed excitation, coherent control and nonlinear spectroscopy was initiated by Taimor and Rice ([17] and references therein). 

A comprehensive discussion of wavepackets, classical-quantum correspondence, optical spectroscopy, coherent control and reactive scattering from a unified, time dependent perspective. 

Figure 39. Pump-dump control of NaK molecule by using two quadratically chirped pulses. The initial state taken as the ground vibrational eigenstate of the ground state X is excited by a quadratically chirped pulse to the excited state A. This excited wavepacket is dumped at the outer turning point at t 230 fs by the second quadratically chirped pulse. The laser parameters used are = 2.75(1.972) X 10-2 eVfs- 1.441(1.031) eV, and / = 0.15(0.10)TWcm-2 for the first (second) pulse. The two pulses are centered at t = 14.5 fs and t2 = 235.8 fs, respectively. Both of them have a temporal width i = 20 fs. (See color insert.) Taken from Ref. [37].

By making use of classical or quantum-mechanical interferences, one can use light to control the temporal evolution of nuclear wavepackets in crystals. An appropriately timed sequence of femtosecond light pulses can selectively excite a vibrational mode. The ultimate goal of such optical control is to prepare an extremely nonequilibrium vibrational state in crystals and to drive it into a novel structural and electromagnetic phase. 

S. P. Shah and S. A. Rice. Controlling quantum wavepacket motion in reduced-dimensional spaces reaction path analysis in optimal control of HCN isomerization. Faraday Trans., 113 319-331(1999). 

The modification of the electronic potentials due to the interaction with the electric field of the laser pulse has another important aspect pertaining to molecules as the nuclear motion can be significantly altered in light-induced potentials. Experimental examples for modifying the course of reactions of neutral molecules after an initial excitation via altering the potential surfaces can be found in Refs 56, 57, where the amount of initial excitation on the molecular potential can be set via Rabi-type oscillations [58]. Nonresonant interaction with an excited vibrational wavepacket can in addition change the population of the vibrational states [59]. Note that this nonresonant Stark control acts on the timescale of the intensity envelope of an ultrashort laser pulse [60]. 

G. Coherence Control of Wavepackets Reactive and Nonreactive Systems... 

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