The 2D Raman-terahertz (THz) response of liquid water is studied in dependence of temperature and isotope substitution (H 2 O, D 2 O, and H 18 2 O). In either case, a very short-lived (i.e., between 75 and 95 fs) echo is observed that reports on the inhomogeneity of the low-frequency intermolecular modes and hence, on the heterogeneity of the hydrogen bond networks of water. The echo lifetime slows down by about 20% when cooling the liquid from room temperature to the freezing point. Furthermore, the echo lifetime of D 2 O is 6.5 ± 1% slower than that of H 2 O, and both can be mapped on each other by introducing an effective temperature shift of ∆T = 4.5 ± 1 K. In contrast, the temperature-dependent echo lifetimes of H 18 2 O and H 2 O are the same within error. D 2 O and H 18 2 O have identical masses, yet H 18 2 O is much closer to H 2 O in terms of nuclear quantum effects. It is, therefore, concluded that the echo is a measure of the structural inhomogeneity of liquid water induced by nuclear quantum effects.water | multidimensional spectroscopy | THz spectroscopy | nuclear quantum effects

A polarizable water model is presented which has been calibrated against experimental THz and Raman spectra of bulk water. These low-frequency spectra directly probe the dynamics, and thereby intermolecular interactions, on time scales relevant to molecular motions. The model is based on the TL4P force field developed recently by Tavan and co-workers [J. Phys. Chem. B 117, 9486 (2013)], which has been designed to be transferable between different environments; in particular, to correctly describe the electrostatic properties of both the isolated water molecule in the gas-phase and the liquid water at ambient conditions. Following this design philosophy, TL4P was amended with charge transfer across hydrogen-bonded dimers as well as an anisotropic polarizability in order to correctly reproduce the THz and Raman spectra. The thermodynamic and structural properties of the new model are of equal quality as those of TL4P, and at the same time, an almost quantitative agreement with the spectroscopic data could be achieved. Since TL4P is a rigid model with a single polarizable site, it is computationally very efficient, while the numerical overhead for the addition of charge transfer and the anisotropic polarizability is minor. Overall, the model is expected to be well suited for, e.g., large scale simulations of 2D-Raman-THz spectra or biomolecular simulations.

2D-Raman-THz spectroscopy of liquid water, which has been presented recently (Proc. Natl. Acad. Sci. USA 110, 20402 (2013)), directly probes the intermolecular degrees of freedom of the hydrogen-bond network. However, being a relatively new technique, its information content is not fully explored as to date. While the spectroscopic signal can be simulated based on molecular dynamics simulation in connection with a water force field, it is difficult to relate spectroscopic signatures to the underlying microscopic features of the force field. Here, a completely different approach is taken that starts from an as simple as possible model, i.e., a single vibrational mode with electrical and mechanical anharmonicity augmented with homogeneous and inhomogeneous broadening. An intuitive Feynman diagram picture is developed for all possible pulse sequences of hybrid 2D-Raman-THz spectroscopy. It is shown that the model can explain the experimental data essentially quantitatively with a very small set of parameters, and it is tentatively concluded that the experimental signal originates from the hydrogen-bond stretching vibration around 170 cm −1 . Furthermore, the echo observed in the experimental data can be quantified by fitting the model. A dominant fraction of its linewidth is attributed to quasi-inhomogeneous broadening in the slowmodulation limit with a correlation time of 370 fs, reflecting the lifetime of the hydrogen-bond networks giving rise the absorption band.

The self-exchange kinetics of CO ligands in the solvated forms of the commonly used complex [MBr3(CO)3](2-) (M = Re, (99)Tc) were investigated in-depth by (13)C NMR spectroscopy in organic solvents such as dimethylformamide and methanol. The two homologues exhibit surprisingly different chemical behavior. In the case of rhenium, the stable intermediate [NEt4][ReBr2(CO)4] was isolated and characterized by (13)C NMR and IR spectroscopy as well as by single-crystal X-ray diffraction. For technetium, no such intermediate could be identified. The activation parameters (ΔH(⧧) = 110 ± 7 kJ mol(-1) and ΔS(⧧) = 127 ± 22 J mol(-1) K(-1)) and the observed influences of different ligands and solvents suggest a dissociative-interchange-type mechanism with a second-order rate constant for the formation of [NEt4][ReBr2(CO)4], k1 = 0.039 ± 0.001 M(-1) s(-1) at 274 K. On the basis of variable-temperature NMR experiments, kinetic simulations, and density functional theory calculations, a complete model for the CO self-exchange, including all respective rate constants, is reported.

The 2D-Raman-THz response in all possible time-orderings (Raman-THz-THz, THz-Raman-THz, and THz-THz-Raman) of amorphous water ice is calculated in two ways: from atomistic molecular dynamics simulations and with the help of a Feynman diagram model, the latter of which power-expands the potential energy surface and the dipole and polarizability surfaces up to leading order. Comparing both results allows one to dissect the 2D-Raman-THz response into contributions from mechanical anharmonicity, as well as electrical dipole and polarizability anharmonicities. Mechanical anharmonicity dominates the 2D-Raman-THz response of the hydrogen-bond stretching and hydrogen-bond bending bands of water, and dipole anharmonicity dominates that of the librational band, while the contribution of polarizability anharmonicity is comparably weak. A distinct echo of the hydrogen-bond stretching band is observed for the THz-Raman-THz pulse sequence, again dominated by mechanical anharmonicity. A peculiar mechanism is discussed, which is based on the coupling between the many normal modes within the hydrogen-bond stretching band and which will inevitably generate such an echo for an amorphous structure.