Vibrational echo correlation spectroscopy a new probe of hydrogen bond dynamics in water and methanol

John B. Asbury, Tobias Steinel, M. D. Fayer

Research output: Chapter in Book/Report/Conference proceedingChapter

1 Scopus citations

Abstract

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 inH2O are studied using the shortest mid-IR pulses (< 45 fs, < 4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (> 400 cm-1) spectrum of the 0-1 and 1-2 vibrational 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. Following hydrogen bond breaking, the broken MeOD oligomers retain a detailed structural memory of the prior intact hydrogen bond network. The correlation spectra are also a sensitive probe of the structural 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 (∼ 100 fs) local fluctuations and essentially identical slower (0.4 ps and ∼ 2 ps) structural rearrangements. Observation of wavelength-dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

Original languageEnglish (US)
Title of host publicationFemtosecond Laser Spectroscopy
PublisherSpringer US
Pages167-196
Number of pages30
ISBN (Print)0387232931, 9780387232935
DOIs
StatePublished - Dec 1 2005

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)

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