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Hiroshi Ushiyama

Publications and source records attributed to Hiroshi Ushiyama.

6 recordsLinked to original sources
PubMed2006

Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: wave-packet dynamics on effective potential surfaces of reduced dimensionality.

We report on a simple but widely useful method for obtaining time-independent potential surfaces of reduced dimensionality wherein the coupling between reaction and substrate modes is embedded by averaging over an ensemble of classical trajectories. While these classically averaged potentials with their reduced dimensionality should be useful whenever a separation between reaction and substrate modes is meaningful, their use brings about significant simplification in studies of time-resolved photoelectron spectra in polyatomic systems where full-dimensional studies of skeletal and photoelectron dynamics can be prohibitive. Here we report on the use of these effective potentials in the studies of dump-probe photoelectron spectra of intramolecular proton transfer in chloromalonaldehyde. In these applications the effective potentials should provide a more realistic description of proton-substrate couplings than the sudden or adiabatic approximations commonly employed in studies of proton transfer. The resulting time-dependent photoelectron signals, obtained here assuming a constant value of the photoelectron matrix element for ionization of the wave packet, are seen to track the proton transfer.

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PubMed2005

Very fast tunneling in the early stage of reaction dynamics.

The difference between quantum and classical survival probabilities for molecular dissociation dynamics in the time domain, which arises mainly from quantum mechanical tunneling, has interesting characteristics that are not noticed through the counterpart in energy domain. It is shown that the early stage undergoes a fast tunneling, while the later stage is characterized with a long-lasting slow tunneling. The mechanism of this behavior is analyzed in terms of a quasi-semiclassical theory featuring the geometrical distribution of the so-called tunneling points. In particular, the role of dynamical tunneling is discussed as a phenomenon that typifies the time dependence of tunneling dynamics. It is predicted that these tunneling characteristics will be reflected in the isotope effect and should be experimentally observable.

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PubMed2005

Extended quantization condition for constructive and destructive interferences and trajectories dominating molecular vibrational eigenstates.

The role of destructive quantum interference in semiclassical quantization of molecular vibrational states is studied. This aspect is crucial for correct quantization, since failure in the appropriate treatment of destructive interference quite often results in many spurious peaks and broad background to hide the true peaks. We first study the time-Fourier transform of the autocorrelation function without performing summation over the trajectories. The resultant quantity, the prespectrum which is a function of individual classical trajectories, provides a clear view about how destructive interference among the trajectories should function. It turns out that the prespectrum is oscillatory but never a random noise. On the contrary, it bears a systematic and regular structure, which is sometimes characterized in terms of very sharp and high peaks in the energy space of the sampled classical trajectories. We have found an extended quantization condition that is responsible for generating these peaks in the prespectrum, which we call the prior quantization condition. Integration of the prespectrum over the trajectory space is supposed to give "zero" (practically a small value of the order of the Planck constant) at a noneigenvalue energy, which is actually a materialization of the destructive interference. Besides, certain finite peaks in the prespectrum survive after the integration to form the true spikes (eigenvalues) in the final spectrum, if they satisfy an additional resonance condition. For these resonance components, the prior quantization condition is reduced to the Einstein-Brillouin-Keller quantization condition. Based on these analyses, we propose a rather conventional filtering technique to efficiently handle tedious computation for destructive interference, and numerically verify that it works well even for multidimensional chaotic systems. This filtering technique is further utilized to extract a few trajectories that dominate an eigenstate of molecular vibration.

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PubMed2004

Time-dependent probability of quantum tunneling in terms of the quasisemiclassical method.

In view of the rapid progress in experiments of the tunneling dynamics in the time domain, we develop a quasisemiclassical method that is aimed at a study of the proton-transfer dynamics in a large system such as tropolone and its interesting derivatives, to which not only full quantum mechanics, but even a standard semiclassical theory is never easy to apply. In our very tractable method for multidimensional systems, the tunneling paths are generated in terms of the generalized classical mechanics, but the quantum phases arising from the action integral, the Maslov index, and the semicalssical amplitude factor as well in the semiclassical kernels are entirely neglected. This approach is called the quasisemiclassical method. One of the technical issues involved in the general semiclassical scheme is how to locate points from which a tunneling path emanates. Hence the studies of such tunneling points and the quasisemiclassical method should be examined collectively. We test several ways of determining the tunneling point, including those already proposed in the literature and a newly proposed one. It is shown numerically that the quasisemiclassical method with an appropriate choice of tunneling points reproduces the full quantum mechanical tunneling probability reasonably well. This case study indicates that the present conventional approach is promising to the study of large systems. The role of tunneling points in the initial process of tunneling is also discussed.

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