Coupling between vibrational modes is essential for energy transfer and dissipation in condensed matter. For water, different O-H stretch modes are known to be very strongly coupled both within and between water molecules, leading to ultrafast dissipation and delocalization of vibrational energy. In contrast, the information on the vibrational coupling of the H-O-H bending mode of water is lacking, even though the bending mode is an essential intermediate for the energy relaxation pathway from the stretch mode to the heat bath. By combining static and femtosecond infrared, Raman, and hyper-Raman spectroscopies for isotopically diluted water with ab initio molecular dynamics simulations, we find the vibrational coupling of the bending mode differs significantly from the stretch mode: the intramode intermolecular coupling of the bending mode is very weak, in stark contrast to the stretch mode. Our results elucidate the vibrational energy transfer pathways of water. Specifically, the librational motion is essential for the vibrational energy relaxation and orientational dynamics of H-O-H bending mode.

We study Raman spectra of ZnO nanoparticles of 5-12 nm size in the whole range of the first-order phonon bands. We apply the 3D phonon confinement model (PCM) for the interpretation of the observed Raman spectra. It is found that PCM is well applicable to the acoustic modes as well as to the optical ones, despite the fact that PCM has been thought not to be suitable for acoustic phonons. We show that the asymptotic behavior of PCM for the small-size limit is more consistent with the observation than that of the elastic sphere model (ESM). Furthermore, PCM gives detailed information on the complex size-dependent shapes of the phonon bands.

An asymmetric fitting function is designed by the damped perturbation of a Voigt profile and tested on systems with different natures of asymmetry.