Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water

  title={Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water},
  author={Christopher J. Fecko and Joel D. Eaves and Joseph J. Loparo and Andrei Tokmakoff and Phillip L. Geissler},
  pages={1698 - 1702}
We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D2O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of… 
Energy transfer in single hydrogen-bonded water molecules.
It is found that the hydrogen bonds in these complexes break and reform with a characteristic time scale of approximately 1 ps, and these hydrogen-bond dynamics are observed to play an important role in the equilibration of vibrational energy over the two O-H groups of the H2O molecule.
The OH stretch vibration of liquid water reveals hydrogen-bond clusters.
It is shown that the high-frequency shoulder, which is most evidently found in Raman spectra of the OH stretch vibration of isotope diluted water, is (at least to a certain extent) related to a three-fold hydrogen-bonded ring.
Pressure Dependence of Hydrogen-Bond Dynamics in Liquid Water Probed by Ultrafast Infrared Spectroscopy.
This work studied, for the first time, the spectral diffusion of the stretching frequency of an HOD impurity in liquid water as a function of pressure, and demonstrates that the rate of spectral diffusion is almost insensitive to the applied pressure.
Local hydrogen bonding dynamics and collective reorganization in water: ultrafast infrared spectroscopy of HOD/D(2)O.
An investigation into hydrogen bonding dynamics and kinetics in water using femtosecond infrared spectroscopy of the OH stretching vibration of HOD in D(2)O finds a kinetic regime which gives an effective rate for exchange of intermolecular structures.
Ultrafast vibrational and structural dynamics of the proton in liquid water.
The dynamical behavior of excess protons in liquid water is investigated using femtosecond vibrational pump-probe spectroscopy and the interconversion between the H9O4 (Eigen) and H5O2(+) (Zundel) hydration structures of the proton is observed.
Hydrogen bond reorganization and vibrational relaxation in water studied with ultrafast infrared spectroscopy
Water consists of an extended hydrogen bond network that is constantly evolving. More than just a description of the time averaged structure is necessary to understand any process that occurs in
Hydrogen Bond Dynamics in Water and Ultrafast Infrared Spectroscopy: A Theoretical Study
Molecular Dynamics simulations are used to examine several key aspects of recent ultrafast infrared experiments on liquid water dynamics in an amplified and extended version of a recent communication
Multidimensional infrared spectroscopy of water. I. Vibrational dynamics in two-dimensional IR line shapes.
The modeling based on fluctuations with Gaussian statistics is able to reproduce the changes in dispersed pump-probe and 2D IR spectra induced by these relaxation processes, but misses the asymmetry resulting from frequency-dependent spectral diffusion.
Direct observation of ultrafast hydrogen bond strengthening in liquid water.
The experiment and simulations unveil the intermolecular character of the water vibration preceding the relaxation of the OH stretch, revealing the need to treat the distribution of the shared proton in the hydrogen bond quantum mechanically to capture the structural dynamics on femtosecond timescales.


Hydrogen Bond Dynamics in Water and Ultrafast Infrared Spectroscopy
Molecular dynamics simulations are used to examine two key aspects of recent ultrafast infrared experiments on liquid water dynamics. It is found that the relation between the OH stretch frequency
Vibrational spectroscopy of HOD in liquid D2O. III. Spectral diffusion, and hydrogen-bonding and rotational dynamics
Time-resolved infrared spectroscopy has the potential to provide unprecedented information about molecular dynamics in liquids. In the case of water, one of the most exciting techniques being
A pump-probe experiment is described to study femtosecond dynamics of hydrogen bonds in liquid water. The key element of the experimental setup is a laser source emitting 150 fs pulses in the 2.5–
Transient absorption of vibrationally excited water
We study the spectral response of the transition between the first and the second excited state of the O–H stretch vibration of HDO dissolved in liquid D2O with two-color femtosecond mid-infrared
Possible Mechanism of OH Frequency Shift Dynamics in Water
The results of the recent infrared pump−probe experiment are analyzed, in which the time evolution of the spectrum of the OH-stretching vibration excited by an ultrashort laser pulse in the dilute
Ultrafast Vibrational Dephasing of Liquid Water
We present the first infrared photon echo study of liquid water. For the O-H stretch vibration of HDO in D{sub 2}O , femtosecond four-wave mixing experiments reveal an extraordinary short pure
The intermolecular dynamics of liquid water
We present the complete intermolecular dynamical spectrum of liquid water, by merging the data sets from femtosecond nonlinear‐optical polarization spectroscopy with the depolarized, Bose–Einstein
Femtosecond solvation dynamics of water
THE timescale of the response of solvent molecules to electronic rearrangement of solute molecules has a critical influence on the rates of chemical reactions in liquids1–10. In particular, if the
A Photon Echo Peak Shift Study of Liquid Water
The first photon echo peak shift study of liquid water is presented. Spectral diffusion within the OH stretching absorption band of HDO in D2O takes place on many time scales with a slow component on