Laser pulses, quantum dynamics

The ability to create and observe coherent dynamics in heterostructures offers the intriguing possibility to control the dynamics of the charge carriers. Recent experiments have shown that control in such systems is indeed possible. For example, phase-locked laser pulses can be used to coherently amplify or suppress THz radiation in a coupled quantum well [5]. The direction of a photocurrent can be controlled by exciting a structure with a laser field and its second harmonic, and then varying the phase difference between the two fields [8,9]. Phase-locked pulses tuned to excitonic resonances allow population control and coherent destruction of heavy hole wave packets [10]. Complex filters can be designed to enhance specific characteristics of the THz emission [11,12]. These experiments are impressive demonstrations of the ability to control the microscopic and macroscopic dynamics of solid-state systems. 

The purpose of this work is to demonstrate that the techniques of quantum control, which were developed originally to study atoms and molecules, can be applied to the solid state. Previous work considered a simple example, the asymmetric double quantum well (ADQW). Results for this system showed that both the wave paeket dynamics and the THz emission can be controlled with simple, experimentally feasible laser pulses. This work extends the previous results to superlattices and chirped superlattices. These systems are considerably more complicated, because their dynamic phase space is much larger. They also have potential applications as solid-state devices, such as ultrafast switches or detectors. 

This chapter discusses the apphcation of femtosecond lasers to the study of the dynamics of molecular motion, and attempts to portray how a synergic combination of theory and experiment enables the interaction of matter with extremely short bursts of light, and the ultrafast processes that subsequently occur, to be understood in terms of fundamental quantum theory. This is illustrated through consideration of a hierarchy of laser-induced events in molecules in the gas phase and in clusters. A speculative conclusion forecasts developments in new laser techniques, highlighting how the exploitation of ever shorter laser pulses would permit the study and possible manipulation of the nuclear and electronic dynamics in molecules. 

Recently, Scherer et al. have used the 10-fs laser pulse with A,excitation = 860 nm to study the dynamical behavior of Rb. Sphaeroides R26 at room temperatures. In this case, due to the use of the 10-fs pulse both P band and B band are coherently excited. Thus the quantum beat behaviors are much more complicated. We have used the data given in Table I and Fig. 19 to simulate the quantum beat behaviors (see also Fig. 22). Without including the electronic coherence, the agreement between experiment and theory can not be accomplished. 

The second dynamical capability of lasers, the ability to excite a large fraction of ground-state molecules to a selected quantum state, has hardly been applied to inorganic systems. To be sure, saturation of excited states by laser pulses is commonplace, but excitation to a selected vibronic level is rare. 

Let us briefly discuss the characteristics of the nonadiabatic dynamics exhibited by this model. Assuming an initial preparation of the S2 state by an ideally short laser pulse. Fig. 1 displays in thick lines the first 500 fs of the quantum-mechanical time evolution of the system. The population probability of the diabatic S2 state shown in Fig. lb exhibits an initial decay on a timescale of 20 fs, followed by quasi-peiiodic recurrences of the population, which are... 

The first volume contained nine state-of-the-art chapters on fundamental aspects, on formalism, and on a variety of applications. The various discussions employ both stationary and time-dependent frameworks, with Hermitian and non-Hermitian Hamiltonian constructions. A variety of formal and computational results address themes from quantum and statistical mechanics to the detailed analysis of time evolution of material or photon wave packets, from the difficult problem of combining advanced many-electron methods with properties of field-free and field-induced resonances to the dynamics of molecular processes and coherence effects in strong electromagnetic fields and strong laser pulses, from portrayals of novel phase space approaches of quantum reactive scattering to aspects of recent developments related to quantum information processing. 

The general theory for the absorption of light and its extension to photodissociation is outlined in Chapter 2. Chapters 3-5 summarize the basic theoretical tools, namely the time-independent and the time-dependent quantum mechanical theories as well as the classical trajectory picture of photodissociation. The two fundamental types of photofragmentation — direct and indirect photodissociation — will be elucidated in Chapters 6 and 7, and in Chapter 8 I will focus attention on some intermediate cases, which are neither truly direct nor indirect. Chapters 9-11 consider in detail the internal quantum state distributions of the fragment molecules which contain a wealth of information on the dissociation dynamics. Some related and more advanced topics such as the dissociation of van der Waals molecules, dissociation of vibrationally excited molecules, emission during dissociation, and nonadiabatic effects are discussed in Chapters 12-15. Finally, we consider briefly in Chapter 16 the most recent class of experiments, i.e., the photodissociation with laser pulses in the femtosecond range, which allows the study of the evolution of the molecular system in real time. 

While such a device has yet to be constructed, Debreczeny and co-workers have synthesized and studied a linear D-A, -A2 triad suitable for implementation in such a device.11641 In this system, compound 6, a 4-aminonaphthalene monoimide (AN I) electron donor is excited selectively with 400 nm laser pulses. Electron transfer from the excited state of ANI to Ai, naphthalene-1,8 4,5-diimide (NI), occurs across a 2,5-dimethylphenyl bridge with x = 420 ps and a quantum yield of 0.95. The dynamics of charge separation and recombination in these systems have been well characterized.11651 Spontaneous charge shift to A2, pyromellitimide (PI), is thermodynamically uphill and does not occur. The mechanism for switching makes use of the large absorption cross-section of the NI- anion radical at 480 nm, (e = 28,300). A second laser pulse at 480 nm can selectively excite this chromophore and provide the necessary energy to move the electron from NI- to PI. These systems do not rely on electrochemical oxidation-reduction reactions at an electrode. Thus, switching occurs on a subpicosecond time scale. 

Equation (7.75) defines what is meant by a so-called coherent sum of quantum states. The diagonal terms resemble the incoherent sum in Eq. (7.74) the values of the populations cn 2 are, however, determined by the laser pulse. The off-diagonal terms are called interference terms these terms are the key to quantum control. They are time dependent and we use the term coherent dynamics for the motion associated with the coherent excitation of quantum states. A particular simple form of Eq. (7.75) is obtained in the special case of two states. Then... 

Figure 5.4, one can easily understand why the interfacial electron transfer should take place in the 10-100 fsec range because this ET process should be faster than the photo-luminescence of the dye molecules and energy transfer between the molecules. Recently Zimmermann et al. [58] have employed the 20 fsec laser pulses to study the ET dynamics in the DTB-Pe/TiC>2 system and for comparison, they have also studied the excited-state dynamics of free perylene in toluene solution. Limited by the 20 fsec pulse-duration, from the uncertainty principle, they can only observe the vibrational coherences (i.e., vibrational wave packets) of low-frequency modes (see Figure 5.5). Six significant modes, 275, 360, 420, 460, 500 and 625 cm-1, have been resolved from the Fourier transform spectra of ultrashort pulse measurements. The Fourier transform spectrum has also been compared with the Raman spectrum. A good agreement can be seen (Figure 5.5). For detail of the analysis of the quantum beat, refer to Figures 5.5-5.7 of Zimmermann et al. s paper [58], These modes should play an important role not only in ET dynamics or excited-state dynamics, but also in absorption spectra. Therefore, the steady state absorption spectra of DTB-Pe, both in...

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