TY - JOUR
T1 - Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol
AU - Asbury, John B.
AU - Steinel, Tobias
AU - Fayer, M. D.
N1 - Funding Information:
We would like to thank Professor James L. Skinner, Department of Chemistry, University of Wisconsin, Madison, for the molecular dynamics simulations of water. We would like to thank Professor Peter Hamm, Physikalisch Chemisches Institut, Universität Zürich, for help with the diagrammatic perturbation theory calculations. This work was supported by the AFOSR (F49620-01-1-0018), DOE (DE-FG03-84ER13251), and NSF (DMR-0332692). TS thanks the Emmy Noether program of the DFG for partial support.
PY - 2004/5
Y1 - 2004/5
N2 - Multidimensional vibrational echo correlation spectroscopy with full phase resolution is used to measure hydrogen bond dynamics in water and methanol. The OD hydroxyl stretches of methanol-OD oligomers in CCl4 and HOD in H2O are studied using the shortest mid-IR pulses (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-1) spectrum of the 0-1 and 1-2 transitions. Hydrogen bond population dynamics are extricated with exceptional detail in MeOD oligomers because the different hydrogen bonded species are spectrally distinct. The experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium relaxation pathway following vibrational relaxation of the hydroxyl stretch. The correlation spectra are also a sensitive probe of the fluctuations in water and provide a stringent test of water models that are widely used in simulations of aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.
AB - Multidimensional vibrational echo correlation spectroscopy with full phase resolution is used to measure hydrogen bond dynamics in water and methanol. The OD hydroxyl stretches of methanol-OD oligomers in CCl4 and HOD in H2O are studied using the shortest mid-IR pulses (<50fs, <4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (>00cm-1) spectrum of the 0-1 and 1-2 transitions. Hydrogen bond population dynamics are extricated with exceptional detail in MeOD oligomers because the different hydrogen bonded species are spectrally distinct. The experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium relaxation pathway following vibrational relaxation of the hydroxyl stretch. The correlation spectra are also a sensitive probe of the fluctuations in water and provide a stringent test of water models that are widely used in simulations of aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen bonded species are subject to distinct (wavelength dependent) ultrafast (∼100fs) local fluctuations and essentially identical slow (0.4 and ∼2ps) structural rearrangements. Observation of wavelength dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.
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U2 - 10.1016/j.jlumin.2003.12.035
DO - 10.1016/j.jlumin.2003.12.035
M3 - Conference article
C2 - 19180255
AN - SCOPUS:1642587279
SN - 0022-2313
VL - 107
SP - 271
EP - 286
JO - Journal of Luminescence
JF - Journal of Luminescence
IS - 1-4
T2 - Proceedings of the 8th International Meeting on Hole Burning, HBSM 2003
Y2 - 26 July 2003 through 31 July 2003
ER -