Wavepacket localization

The method of electronic excitation by a quadratically chirped pulse mentioned above can be applied to a wavepacket moving away from the turning point, so this technique can be applied to various processes such as pump-dump, wavepacket localization and selective bond-breaking, as we will discuss in the rest of this section. 

Fig. 9. Demonstration of the capability of the OCT to create wavepackets localized in nearly arbitrary regions.

In order to localize the particle, it is necessary to superimpose wavefiinctions i with different momenta k. A very general way to do this is to construct a wavepacket, defined tlirough the integral... 

It is not difficult to show that, for a constant potential, equation (A3.11.218) and equation (A3.11.219) can be solved to give the free particle wavepacket in equation (A3.11.7). More generally, one can solve equation (A3.11.218) and equation (A3.11.219) numerically for any potential, even potentials that are not quadratic, but the solution obtained will be exact only for potentials that are constant, linear or quadratic. The deviation between the exact and Gaussian wavepacket solutions for other potentials depends on how close they are to bemg locally quadratic, which means... 

In a time-dependent picture, resonances can be viewed as localized wavepackets composed of a superposition of continuum wavefimctions, which qualitatively resemble bound states for a period of time. The unimolecular reactant in a resonance state moves within the potential energy well for a considerable period of time, leaving it only when a fairly long time interval r has elapsed r may be called the lifetime of the almost stationary resonance state. 

The experiment is illustrated in figure B2.5.9. The initial pump pulse generates a localized wavepacket in the first excited state of Nal, which evolves with time. The potential well in the state is the result of an avoided crossing with the ground state. Every time the wavepacket passes this region, part of it crosses to the lower surface before the remainder is reflected at the outer wall of the potential. The crossing leads to... 

As in previous sections, the zeros of l (x, t) in the complex t plane at fixed x are of interest. This appears a hopeless task, but the situation is not that bleak. Thus, let us consider a wavepacket initially localized in the ground state in the sense that in Eq. (50), for some given x. 

A different approach is to represent the wavepacket by one or more Gaussian functions. When using a local harmonic approximation to the trae PES, that is, expanding the PES to second-order around the center of the function, the parameters for the Gaussians are found to evolve using classical equations of motion [22-26], Detailed reviews of Gaussian wavepacket methods are found in [27-29]. 

In the full quantum mechanical picture, the evolving wavepackets are delocalized functions, representing the probability of finding the nuclei at a particular point in space. This representation is unsuitable for direct dynamics as it is necessary to know the potential surface over a region of space at each point in time. Fortunately, there are approximate formulations based on trajectories in phase space, which will be discussed below. These local representations, so-called as only a portion of the FES is examined at each point in time, have a classical flavor. The delocalized and nonlocal nature of the full solution of the Schtddinger equation should, however, be kept in mind. 

A technical difference from other Gaussian wavepacket based methods is that the local hamionic approximation has not been used to evaluate any integrals, but instead Maiti nez et al. use what they term a saddle-point approximation. This uses the localization of the functions to evaluate the integrals by... 

To uniquely associate the unusual behavior of the collision observables with the existence of a reactive resonance, it is necessary to theoretically characterize the quantum state that gives rise to the Lorentzian profile in the partial cross-sections. Using the method of spectral quantization (SQ), it is possible to extract a Seigert state wavefunction from time-dependent quantum wavepackets using the Fourier relation Eq. (21). The state obtained in this way for J = 0 is shown in Fig. 7 this state is localized in the collinear F — H — D arrangement with 3-quanta of excitation in the asymmetric stretch mode, and 0-quanta of excitation in the bend and symmetric stretch modes. If the state pictured in Fig. 7 is used as an initial (prepared) state in a wavepacket calculation, one observes pure... 

The initial wavefunction is a product of a specific rovibrational eigenfunction for the reactants and a localized translational wavepacket for R ... 

Similar to the diatom-diatom reaction, the initial wavefunction is chosen as the direct product of a localized translational wavepacket for R and a specific (JMe) state for the atom-triatom system with a specific rovibrational eigenstate (z/o, Lo,Bo) f°r the triatom ABC ... 

One can also ask about the relationship of the FMS method, as opposed to AIMS, with other wavepacket and semiclassical nonadiabatic dynamics methods. We first compare FMS to previous methods in cases where there is no spawning, and then proceed to compare with previous methods for nonadiabatic dynamics. We stress that we have always allowed for spawning in our applications of the method, and indeed the whole point of the FMS method is to address problems where localized nuclear quantum mechanical effects are important. Nevertheless, it is useful to place the method in context by asking how it relates to previous methods in the absence of its adaptive basis set character. There have been many attempts to use Gaussian basis functions in wavepacket dynamics, and we cannot mention all of these. Instead, we limit ourselves to those methods that we feel are most closely related to FMS, with apologies to those that are not included. A nice review that covers some of the... 

One expects the timescale of the nonadiabatic transition to broaden for a stationary initial state, where the nuclear wavepacket will be less localized. To mimic the case of a stationary initial state, we have averaged the results of 25 nonstationary initial conditions and the resulting ground-state population is shown as the dashed line in Fig. 8. The expected broadening is seen, but the nonadiabatic events are still close to the impulsive limit. Additional averaging of the results would further smooth the dashed line. 

When 0 < 0 the photon wavepackets that are lined up after each other on the same axis can match their phases and combine into more elongated packets. As a result the linewidth of a single photon is expected to become larger than that of a dense photon beam. The local energy flux density v / should at the same time be given by the number of photons passing a cross-sectional area, regardless of the value of the ratio 0 . 

It seems quite natural to describe the extended part of a quantum particle not by wavepackets composed of infinite harmonic plane waves but instead by finite waves of a well-defined frequency. To a person used to the Fourier analysis, this assumption—that it is possible to have a finite wave with a well-defined frequency—may seem absurd. We are so familiar with the Fourier analysis that when we think about a finite pulse, we immediately try to decompose, to analyze it into the so-called pure frequencies of the harmonic plane waves. Still, in nature no one has ever seen a device able to produce harmonic plane waves. Indeed, this concept would imply real physical devices existing forever with no beginning or end. In this case it would be necessary to have a perfect circle with an endless constant motion whose projection of a point on the centered axis gives origin to the sine or cosine harmonic function. This would mean that we should return to the Ptolemaic model for the Havens, where the heavenly bodies localized on the perfect crystal balls turning in constant circular motion existed from continuously playing the eternal and ethereal harmonic music of the spheres. 

The explanation for the absence of interference comes naturally from the causal model of a particle whose undulatory part is described by a finite localized wavelet. In this situation, the limitless spreading of matter wavepackets originates from the fact that in the initial burst, coming from the source, each individual localized quantum particle travels at a different velocity. Therefore, as the time increases the distance among them also increases, as shown in Fig. 24. 

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