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Acc Chem Res. 2009 Sep 15;42(9):1270-9. doi: 10.1021/ar9000444.

Modeling, calculating, and analyzing multidimensional vibrational spectroscopies.

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1
Department of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa, Sakyoku, Kyoto 606-8502, Japan. tanimura@kuchem.kyoto-u.ac.jp

Abstract

Spectral line shapes in a condensed phase contain information from various dynamic processes that modulate the transition energy, such as microscopic dynamics, inter- and intramolecular couplings, and solvent dynamics. Because nonlinear response functions are sensitive to the complex dynamics of chemical processes, multidimensional vibrational spectroscopies can separate these processes. In multidimensional vibrational spectroscopy, the nonlinear response functions of a molecular dipole or polarizability are measured using ultrashort pulses to monitor inter- and intramolecular vibrational motions. Because a complex profile of such signals depends on the many dynamic and structural aspects of a molecular system, researchers would like to have a theoretical understanding of these phenomena. In this Account, we explore and describe the roles of different physical phenomena that arise from the peculiarities of the system-bath coupling in multidimensional spectra. We also present simple analytical expressions for a weakly coupled multimode Brownian system, which we use to analyze the results obtained by the experiments and simulations. To calculate the nonlinear optical response, researchers commonly use a particular form of a system Hamiltonian fit to the experimental results. The optical responses of molecular vibrational motions have been studied in either an oscillator model or a vibration energy state model. In principle, both models should give the same results as long as the energy states are chosen to be the eigenstates of the oscillator model. The energy state model can provide a simple description of nonlinear optical processes because the diagrammatic Liouville space theory that developed in the electronically resonant spectroscopies can easily handle three or four energy states involved in high-frequency vibrations. However, the energy state model breaks down if we include the thermal excitation and relaxation processes in the dynamics to put the system in a thermal equilibrium state. The roles of these excitation and relaxation processes are different and complicated compared with those in the resonant spectroscopy. Observing the effects of such thermal processes is more intuitive with the oscillator model because the bath modes, which cause the fluctuation and dissipation processes, are also described in the coordinate space. This coordinate space system-bath approach complements a realistic full molecular dynamics simulation approach. By comparing the calculated 2D spectra from the coordinate space model and the energy state model, we can examine the role of thermal processes and anharmonic mode-mode couplings in the energy state model. For this purpose, we employed the Brownian oscillator model with the nonlinear system-bath interaction. Using the hierarchy formalism, we could precisely calculate multidimensional spectra for a single and multimode anharmonic system for inter- and intramolecular vibrational modes.

PMID:
19441802
DOI:
10.1021/ar9000444
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