Nonequilibrium molecular dynamics simulations with a backward-forward trajectories sampling for multidimensional infrared spectroscopy of molecular vibrational modes

Department of Chemistry, Graduate School of Science, Kyoto University, Sakyoku, Kyoto 606-8502, Japan.
The Journal of Chemical Physics (Impact Factor: 2.95). 03/2008; 128(6):064511. DOI: 10.1063/1.2828189
Source: PubMed


A full molecular dynamics (MD) simulation approach to calculate multidimensional third-order infrared (IR) signals of molecular vibrational modes is proposed. Third-order IR spectroscopy involves three-time intervals between three excitation and one probe pulses. The nonequilibrium MD (NEMD) simulation allows us to calculate molecular dipoles from nonequilibrium MD trajectories for different pulse configurations and sequences. While the conventional NEMD approach utilizes MD trajectories started from the initial equilibrium state, our approach does from the intermediate state of the third-order optical process, which leads to the doorway-window decomposition of nonlinear response functions. The decomposition is made before the second pump excitation for a two-dimensional case of IR photon echo measurement, while it is made after the second pump excitation for a three-dimensional case of three-pulse IR photon echo measurement. We show that the three-dimensional IR signals are efficiently calculated by using the MD trajectories backward and forward in time for the doorway and window functions, respectively. We examined the capability of the present approach by evaluating the signals of two- and three-dimensional IR vibrational spectroscopies for liquid hydrogen fluoride. The calculated signals might be explained by anharmonic Brownian model with the linear-linear and square-linear system-bath couplings which was used to discuss the inhomogeneous broadening and dephasing mechanism of vibrational motions. The predicted intermolecular librational spectra clearly reveal the unusually narrow inhomogeneous linewidth due to the one-dimensional character of HF molecule and the strong hydrogen bond network.

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Available from: Yoshitaka Tanimura, Oct 06, 2015
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    • "As a result, the application of AIMD simulations has been limited to computing the static vibrational spectra of water and solutes in water [31] [32] [33] [34] [35]. On the other hand, some pioneering classical force-field nonequilibrium MD (NEMD) simulations have succeeded in computing the vibrational dynamics followed by the vibrational excitation by tracing the excess kinetic energy relaxation [36] [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] as well as the electrostatic mapping technique [47]; however, they may present a biased view as they do not account for the anharmonicity and delocalization of the vibrational modes from electronic structure theory, which is, in particular, critical for the O-H stretch mode in bulk H 2 O. "
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    ABSTRACT: Water is a unique solvent with strong, yet highly dynamic, intermolecular interactions. Many insights into this distinctive liquid have been obtained using ultrafast vibrational spectroscopy of water's O-H stretch vibration. However, it has been challenging to separate the different contributions to the dynamics of the O-H stretch vibration in H 2 O. Here, we present a novel nonequilibrium molecular dynamics (NEMD) algorithm that allows for a detailed picture of water vibrational dynamics by generating nonequilibrium vibrationally excited states at targeted vibrational frequencies. Our ab initio NEMD simulations reproduce the experimentally observed time scales of vibrational dynamics in H 2 O. The approach presented in this work uniquely disentangles the effects on the vibrational dynamics of four contributions: the delocalization of the O-H stretch mode, structural dynamics of the hydrogen bonded network, intramolecular coupling within water molecules, and intermolecular coupling between water molecules (near-resonant energy transfer between O-H groups). Our results illustrate that intermolecular energy transfer and the delocalization of the O-H stretch mode are particularly important for the spectral diffusion in H 2 O.
    Physical Review X 04/2015; 5(2):021002. DOI:10.1103/PhysRevX.5.021002 · 9.04 Impact Factor
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    ABSTRACT: Physical and chemical properties of liquid water are dominated by hydrogen bond structure and dynamics. Recent studies on nonlinear vibrational spectroscopy of intramolecular motion provided new insight into ultrafast hydrogen bond dynamics. However, our understanding of intermolecular dynamics of water is still limited. We theoretically investigated the intermolecular dynamics of liquid water in terms of two-dimensional infrared (2D IR) spectroscopy. The 2D IR spectrum of intermolecular frequency region (<1000 cm(-1)) is calculated by using the equilibrium and nonequilibrium hybrid molecular dynamics method. We find the ultrafast loss of the correlation of the libration motion with the time scale of approximately 110 fs. It is also found that the energy relaxation from the libration motion to the low frequency motion takes place with the time scale of about 180 fs. We analyze the effect of the hindered translation motion on these ultrafast dynamics. It is shown that both the frequency modulation of libration motion and the energy relaxation from the libration to the low frequency motion significantly slow down in the absence of the hindered translation motion. The present result reveals that the anharmonic coupling between the hindered translation and libration motions is essential for the ultrafast relaxation dynamics in liquid water.
    The Journal of Chemical Physics 04/2008; 128(15):154521. DOI:10.1063/1.2903470 · 2.95 Impact Factor
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    ABSTRACT: A model for the dipolar crystal system is employed to explore a role of free energy landscape (FEL), in which dipolar molecules are posted on two-dimensional lattice sites with two-state libratinal dynamics. All dipole-dipole interactions are included to have frustrated interactions among the dipoles. For the regular and distorted lattice cases, the FEL is calculated from the interaction energies and the total polarizations for all possible dipolar states at various temperatures. At high temperatures, the shape of the calculated FEL is smooth and parabolic, while it becomes bumpy at low temperatures exhibiting multiple local minima. To study dynamical aspects of the system, the single flip dynamics and the single-double mixed flips dynamics of dipoles are examined from a master equation approach. As the observables of linear absorption and two-dimensional (2D) infrared, far infrared, and terahertz spectroscopies, the first- and third-order response functions of polarization are calculated for different physical conditions characterized by the FEL. While the linear absorption signals decay in time in a similar manner regardless of the FEL profiles, the 2D signals exhibit prominent differences for those profiles. This indicates that we may differentiate the FEL profiles by changing two-time valuables in 2D spectroscopy. As illustrated in the single-double flips case, the FEL study by means of 2D spectroscopy, however, relies on the dynamics which is set independently from the FEL. The Smoluchowski equation is applied to examine the description of the collective dynamics on the microscopically calculated FEL. We found that the one-dimensional and 2D signals calculated from the Smoluchowski equation agree with those from master equation only at temperatures where the FEL becomes parabolic shape.
    The Journal of Chemical Physics 05/2008; 128(16):164501. DOI:10.1063/1.2897982 · 2.95 Impact Factor
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