Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O

  title={Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O},
  author={Michael L. Cowan and Barry D. Bruner and Nils Huse and Jason R. Dwyer and Brige P. Chugh and Erik T. J. Nibbering and Thomas Elsaesser and R. J. Dwayne Miller},
Many of the unusual properties of liquid water are attributed to its unique structure, comprised of a random and fluctuating three-dimensional network of hydrogen bonds that link the highly polar water molecules. One of the most direct probes of the dynamics of this network is the infrared spectrum of the OH stretching vibration, which reflects the distribution of hydrogen-bonded structures and the intermolecular forces controlling the structural dynamics of the liquid. Indeed, water dynamics… 

Anharmonic exciton dynamics and energy dissipation in liquid water from two-dimensional infrared spectroscopy.

This paper presents a comprehensive analysis of the two-dimensional infrared spectrum of O-H stretching vibrations in liquid H2O and their interactions with bending and intermolecular vibrations and argues that the collective nature of water vibrations should be considered in describing aqueous solvation.

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

Molecular dynamics simulation of nonlinear spectroscopies of intermolecular motions in liquid water.

These theoretical methods do not require frequently used assumptions and can thus be called ab initio methods; together with multidimensional nonlinear spectroscopies, they provide powerful methods for examining the inter- and intramolecular details of water dynamics.

Ultrafast memory loss and relaxation processes in hydrogen-bonded systems

Vibrational spectroscopy in the femtosecond time domain is applied to map structural dynamics in real-time and identify underlying molecular interactions in an aqueous environment that displays an ultrafast loss of structural memory.

Femtosecond mid-infrared study of the reorientation of weakly hydrogen-bonded water molecules.

It is observed that with increasing temperature, the spectral relaxation shows a similar acceleration as the average molecular reorientation, showing that these processes are intimately connected.

Energy transfer within the hydrogen bonding network of water following resonant terahertz excitation

The dynamic energy flow in the hydrogen bond network of liquid water is investigated by a pump-probe experiment that resonantly excites intermolecular degrees of freedom with ultrashort single-cycle terahertz pulses and monitors its Raman response.

Structural rearrangements in water viewed through two-dimensional infrared spectroscopy.

This Account reviews recent ultrafast 2D IR studies at MIT that provide new information on the mechanism of hydrogen-bond rearrangements in liquid water, and demonstrates a more general, unique characteristic of the spectroscopy: if a spectral signature of the transition state exists, then 2DIR can effectively serve as a transition-state spectroscope.

Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.

  • T. Elsaesser
  • Chemistry, Physics
    Accounts of chemical research
  • 2009
This Account reviews recent progress originating from third-order nonlinear methods of coherent multidimensional vibrational spectroscopy and expects that the application of 2D infrared Spectroscopy in an extended spectral range will reveal the intrinsic coupling between water and specific functional units of DNA.

Ultrafast intermolecular dynamics of liquid water: a theoretical study on two-dimensional infrared spectroscopy.

The present result reveals that the anharmonic coupling between the hindered translation and libration motions is essential for the ultrafast relaxation dynamics in liquid water.

Equilibrium and mid-infrared driven vibrational dynamics of artificial hydrogen-bonded networks.

This finding supports a mechanism for vibrational energy relaxation in all-syn polyols that is mediated by hydrogen-bond dissociation within 850 fs, and can be understood in terms of pure intramolecular vibrational relaxation occurring with a time constant of 1.3 ps.



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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

Femtosecond Dynamics of Hydrogen Bonds in Liquid Water: A Real Time Study

An experiment is described to study temporal variations of the hydrogen bond length in diluted HDO/D2O solutions. The principles of this laser spectroscopic experiment are explained first. The

Hydrogen-bond kinetics in liquid water

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Water Dynamics: Vibrational Echo Correlation Spectroscopy and Comparison to Molecular Dynamics Simulations

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The nature of the hydrated excess proton in water

Explanations for the anomalously high mobility of protons in liquid water began with Grotthuss's idea, of ‘structural diffusion’ nearly two centuries ago. Subsequent explanations have refined this

Vibrational spectroscopy of HOD in liquid D2O. II. Infrared line shapes and vibrational Stokes shift

We present semiclassical calculations of the infrared line shapes for the three intramolecular vibrations of dilute HOD in liquid D2O. In these calculations the vibrations of HOD are treated quantum

Comparison of the structure of harmonic aqueous glasses and liquid water.

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Structural relaxation in supercooled water by time-resolved spectroscopy

Time-resolved optical Kerr effect measurements are reported that unambiguously demonstrate that the structural relaxation of liquid and weakly supercooled water follows the behaviour predicted by simple mode-coupling theory, supporting the interpretation of the singularity as a purely dynamical transition.