Pressure Dependence of Hydrogen-Bond Dynamics in Liquid Water Probed by Ultrafast Infrared Spectroscopy

Year: 2016

Authors: Lapini A., Pagliai M., Fanetti S., Citroni M., Scandolo S ., Bini R., Righini R.

Autors Affiliation: European Lab Nonlinear Spect, LENS, Via N Carrara 1, I-50019 Florence, Italy;‎ Univ Florence, Dipartimento Chim Ugo Schiff, Via Lastruccia 3, I-50019 Florence, Italy; Abdus Salam Int Ctr Theoret Phys ICTP, I-34151 Trieste, Italy;‎ CNR, INO, Largo Fermi 6, I-50125 Florence, Italy;‎ CNR, Ist Chim Composti Organometallici ICCOM, Via Madonna del Piano 10, I-50019 Sesto Fiorentino, Italy; Scuola Normale Super Pisa, Piazza Cavalieri 7, I-56126 Pisa, Italy

Abstract: Clarifying the structure/dynamics relation of water hydrogen-bond network has been the aim of extensive research over many decades. By joining anvil cell high-pressure technology, femtosecond 2D infrared spectroscopy, and molecular dynamics simulations, we studied, for the first time, the spectral diffusion of the stretching frequency of an HOD impurity in liquid water as a function of pressure. Our experimental and simulation results concordantly demonstrate that the rate of spectral diffusion is almost insensitive to the applied pressure. This behavior is in contrast with the previously reported pressure-induced speed up of the orientational dynamics, which can be rationalized in terms of large angular jumps involving sudden switching between two hydrogen-bonded configurations. The different trend of the spectral diffusion can be, instead, inferred considering that the first solvation shell preserves the tetrahedral structure with pressure and the OD stretching frequency is only slight perturbed.


Volume: 7 (18)      Pages from: 3579  to: 3584

More Information: We acknowledge the Deep Carbon Observatory initiative (grant “Extreme Physics and Chemistry of Carbon, Transformation and Movements in Planetry Interiors” from the Alfred P. Sloan Foundation) and MIUR (grants FIRB – Futuro in Ricerca 2010 RBFR109ZHQ and RBFR10Y5VW).
KeyWords: Hydrogen-Bond Dynamics, Ultrafast Infrared Spectroscopy
DOI: 10.1021/acs.jpclett.6b01375

Citations: 16
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