cad a22 4500 555301117 20190207033959.0 cr unu---uuuuu 190206e20190128xx s 000 0 eng 10.5167/uzh-161657 doi 10.1063/1.5079497 doi (ZORA)oai:www.zora.uzh.ch:161657 540 ddc Hamm Peter Feynman Diagram Description of 2D-Raman-THz Spectroscopy Applied to Water [Elektronische Daten] [Peter Hamm, David Sidler] openAccess eu-repo 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. Department of Chemistry zora Sidler David joint author Journal of Chemical Physics 150(4):044202 https://www.zora.uzh.ch/id/eprint/161657/1/Pr-Print.pdf text/html WWW-Backlink auf das Repository 1 Journal Article PeerReviewed zora ZORA 856 40 https://www.zora.uzh.ch/id/eprint/161657/1/Pr-Print.pdf text/html WWW-Backlink auf das Repository ZORA 100 1- Hamm Peter ZORA 700 1- Sidler David joint author ZORA 773 0- Journal of Chemical Physics 150(4):044202 BK010053 XK010053 XK010000 ZORA ZORA ZORA Journal Article openAccess