title: Fifth-order two-dimensional Raman spectroscopy of liquid water, crystalline ice Ih and amorphous ices: sensitivity to anharmonic dynamics and local hydrogen bond network structure.
abstract: The theoretical study of off-resonant fifth-order two-dimensional (2D)-Raman spectroscopy is made to analyze the intermolecular dynamics of liquid and solid water. The 2D-Raman spectroscopy is susceptible to the nonlinear anharmonic dynamics and local hydrogen bond structure in water. It is found that the distinct 2D-Raman response appears as the negative signal near the t(2) axis. The origin of this negative signal for t(2)<15 fs is from the nonlinear polarizability in the librational motions, whereas that for 30 fs<t(2)<150 fs is attributed to the anharmonic translational motions. It is found that the mechanical anharmonicity and nonlinear polarizability couplings among modes clearly can be observed as the sum- and difference-frequency peaks in the 2D-Raman spectrum (i.e., Fourier transforms of the response). The 2D-Raman spectroscopies of ice Ih and amorphous ices, i.e., low density, high density, and very high density amorphous ices, are also investigated. It is found that the 2D-Raman spectroscopy is very sensitive to the anisotropy of the structure of ice Ih. The strong hydrogen bond stretching band is seen in the 2D-Raman spectroscopy of the polarization directions parallel to the c axis, whereas the contributions of the librational motion can be also seen in the spectrum with the polarization directions parallel to the a axis. The 2D-Raman spectroscopy is also found to be also very sensitive to the differences in local hydrogen bond network structures in various amorphous phases.
authors.affiliation: Department of Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki, Aichi 444-8585, Japan. shinji@ims.ac.jp
authors.forename: Shinji
authors.initials: S
authors.lastname: Saito
authors.forename: Iwao
authors.initials: I
authors.lastname: Ohmine