Calculating Multidimensional Optical Spectra from Classical Trajectories.

Multidimensional optical spectra are measured from the response of a material system to a sequence of laser pulses and have the capacity to elucidate specific molecular interactions and dynamics whose influences are absent or obscured in a conventional linear absorption spectrum. Interpretation of complex spectra is supported by theoretical modeling of the spectroscopic observable, requiring implementation of quantum dynamics for coupled electrons and nuclei. Performing numerically correct quantum dynamics in this context may pose computational challenges, particularly in the condensed phase. Semiclassical methods based on calculating classical trajectories offer a practical alternative. Here I review the recent application of some semiclassical, trajectory-based methods to nonlinear molecular vibrational and electronic spectra.

Quantum Chaos in the Dynamics of Molecules.

Quantum chaos is reviewed from the viewpoint of "what is molecule?", particularly placing emphasis on their dynamics. Molecules are composed of heavy nuclei and light electrons, and thereby the very basic molecular theory due to Born and Oppenheimer gives a view that quantum electronic states provide potential functions working on nuclei, which in turn are often treated classically or semiclassically. Therefore, the classic study of chaos in molecular science began with those nuclear dynamics particularly about the vibrational energy randomization within a molecule. Statistical laws in probabilities and rates of chemical reactions even for small molecules of several atoms are among the chemical phenomena requiring the notion of chaos. Particularly the dynamics behind unimolecular decomposition are referred to as Intra-molecular Vibrational energy Redistribution (IVR). Semiclassical mechanics is also one of the main research fields of quantum chaos. We herein demonstrate chaos that appears only in semiclassical and full quantum dynamics. A fundamental phenomenon possibly giving birth to quantum chaos is "bifurcation and merging" of quantum wavepackets, rather than "stretching and folding" of the baker's transformation and the horseshoe map as a geometrical foundation of classical chaos. Such wavepacket bifurcation and merging are indeed experimentally measurable as we showed before in the series of studies on real-time probing of nonadiabatic chemical reactions. After tracking these aspects of molecular chaos, we will explore quantum chaos found in nonadiabatic electron wavepacket dynamics, which emerges in the realm far beyond the Born-Oppenheimer paradigm. In this class of chaos, we propose a notion of Intra-molecular Nonadiabatic Electronic Energy Redistribution (INEER), which is a consequence of the chaotic fluxes of electrons and energy within a molecule.