Asbury, John B.; Steinel, Tobias; Stromberg, C.; Corcelli, S. A.; Lawrence, C. P.; Skinner, J. L.; Fayer, M. D.
Water Dynamics: Vibrational Echo Correlation Spectroscopy and Comparison to Molecular Dynamics Simulations
The dynamics of water are examd. using ultrafast IR stimulated vibrational echo correlation spectroscopy. The OD hydroxyl stretch of HOD in H2O is probed with 45-fs pulses that have sufficient bandwidth (>400 cm-1) to span the entire broad spectrum. High-quality 2D correlation spectra are obtained having the correct phase relations across the broad hydroxyl band. The correlation spectra are found to evolve on multiple time scales. The time evolution of the vibrational echo correlation spectrum reflects the structural evolution of the hydrogen bond networks. The extended vibrational lifetime of the OD hydroxyl stretch of HOD in H2O facilitates the measurement of hydrogen bond dynamics for longer times than possible in previous studies of the OH stretch. Mol. dynamics simulations/electronic structure calcns. are used to obtain the time correlation functions (TCF) for two water models, TIP4P and SPC/E. The TCFs are inputs to full time-dependent diagrammatic perturbation theory calcns., which yield theor. correlation spectra. Quant. comparison with the data demonstrates that the two water models somewhat overemphasize the fast fluctuations in water and do not contain a slow enough component to account for the slowest fluctuations. Fits to the data using a phenomenol. triexponential TCF yield a slowest component of âˆ¼2 ps, and TIP4P and SPC/E have slowest components of <1 ps. The TCF obtained from the water models and the triexponential TCF reproduce the linear absorption line shape equally well, but all miss to some extent the asym. "wing" on the low-energy side of the line. Therefore, the time dependence of the vibrational echo correlation spectra provides a good test for the TCF, but the absorption spectrum does not. [on SciFinder(R)]
Stretching vibration (OD, of HDO water dynamics studied by vibrational echo correlation spectroscopy and comparison to mol. dynamics simulations) IR spectra (two-dimensional water dynamics studied by vibrational echo correlation spectroscopy and comparison to mol. dynamics simulations) Photon echo (vibrational water dynamics studied by vibrational echo correlation spectroscopy and comparison to mol. dynamics simulations) water dynamics vibrational echo correlation spectroscopy
CAN 140:171315 73-3 Optical, Electron, and Mass Spectroscopy and Other Related Properties Department of Chemistry, Stanford University, Stanford, CA, USA. Journal 1089-5639 7732-18-5 (Water); 14940-63-7 (Water-d) Role: PRP (Properties) (water dynamics studied by vibrational echo correlation spectroscopy and comparison to mol. dynamics simulations)