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Title: Interference effects in IR photon echo spectroscopy of liquid water

Abstract

Heterodyne-detected transient grating experiments on the OH-stretch mode of HDO dissolved in D{sub 2}O resolve two distinctly different contributions originating from the initially excited OH stretch and the OD stretch which is thermally activated during the OH population relaxation. It is demonstrated that interference of both contributions greatly affects the outcome of IR photon echo experiments.

Authors:
; ;  [1]
  1. Ultrafast Laser and Spectroscopy Laboratory, Materials Science Centre, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands)
Publication Date:
OSTI Identifier:
20979292
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. A; Journal Volume: 73; Journal Issue: 2; Other Information: DOI: 10.1103/PhysRevA.73.021804; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; HEAVY WATER; INTERFERENCE; LIQUIDS; PHOTONS; RELAXATION; SPECTROSCOPY; TRANSIENTS

Citation Formats

Yeremenko, Sergey, Pshenichnikov, Maxim S., and Wiersma, Douwe A.. Interference effects in IR photon echo spectroscopy of liquid water. United States: N. p., 2006. Web. doi:10.1103/PHYSREVA.73.021804.
Yeremenko, Sergey, Pshenichnikov, Maxim S., & Wiersma, Douwe A.. Interference effects in IR photon echo spectroscopy of liquid water. United States. doi:10.1103/PHYSREVA.73.021804.
Yeremenko, Sergey, Pshenichnikov, Maxim S., and Wiersma, Douwe A.. Wed . "Interference effects in IR photon echo spectroscopy of liquid water". United States. doi:10.1103/PHYSREVA.73.021804.
@article{osti_20979292,
title = {Interference effects in IR photon echo spectroscopy of liquid water},
author = {Yeremenko, Sergey and Pshenichnikov, Maxim S. and Wiersma, Douwe A.},
abstractNote = {Heterodyne-detected transient grating experiments on the OH-stretch mode of HDO dissolved in D{sub 2}O resolve two distinctly different contributions originating from the initially excited OH stretch and the OD stretch which is thermally activated during the OH population relaxation. It is demonstrated that interference of both contributions greatly affects the outcome of IR photon echo experiments.},
doi = {10.1103/PHYSREVA.73.021804},
journal = {Physical Review. A},
number = 2,
volume = 73,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2006},
month = {Wed Feb 15 00:00:00 EST 2006}
}
  • Vibrational spectroscopy is frequently used to characterize nanoconfined liquids and probe the effect of the confining framework on the liquid structure and dynamics relative to the corresponding bulk fluid. However, it is still unclear what molecular-level information can be obtained from such measurements. In this paper, we address this question by using molecular dynamics (MD) simulations to reproduce the linear infrared (IR), Raman, and two-dimensional IR (2D-IR) photon echo spectra for water confined within hydrophilic (hydroxyl-terminated) silica mesopores. To simplify the spectra the OH stretching region of isotopically dilute HOD in D{sub 2}O is considered. An empirical mapping approach ismore » used to obtain the OH vibrational frequencies, transition dipoles, and transition polarizabilities from the MD simulations. The simulated linear IR and Raman spectra are in good general agreement with measured spectra of water in mesoporous silica reported in the literature. The key effect of confinement on the water spectrum is a vibrational blueshift for OH groups that are closest to the pore interface. The blueshift can be attributed to the weaker hydrogen bonds (H-bonds) formed between the OH groups and silica oxygen acceptors. Non-Condon effects greatly diminish the contribution of these OH moieties to the linear IR spectrum, but these weaker H-bonds are readily apparent in the Raman spectrum. The 2D-IR spectra have not yet been measured and thus the present results represent a prediction. The simulated spectra indicates that it should be possible to probe the slower spectral diffusion of confined water compared to the bulk liquid by analysis of the 2D-IR spectra.« less
  • Vibrational spectroscopy is frequently used to characterize nanoconfined liquids and probe the effect of the confining framework on the liquid structure and dynamics relative to the corresponding bulk fluid. However, it is still unclear what molecular-level information can be obtained from such measurements. In this Paper, we address this question by using molecular dynamics (MD) simulations to reproduce the linear infrared (IR), Raman, and two-dimensional IR (2D-IR) photon echo spectra for water confined within hydrophilic (hydroxyl-terminated) silica mesopores. To simplify the spectra the OH stretching region of isotopically dilute HOD in D 2O is considered. An empirical mapping approach ismore » used to obtain the OH vibrational frequencies, transition dipoles, and transition polarizabilities from the MD simulations. The simulated linear IR and Raman spectra are in good general agreement with measured spectra of water in mesoporous silica reported in the literature. The key effect of confinement on the water spectrum is a vibrational blueshift for OH groups that are closest to the pore interface. The blueshift can be attributed to the weaker hydrogen bonds (H-bonds) formed between the OH groups and silica oxygen acceptors. Non-Condon effects greatly diminish the contribution of these OH moieties to the linear IR spectrum, but these weaker H-bonds are readily apparent in the Raman spectrum. The 2D-IR spectra have not yet been measured and thus the present results represent a prediction. Lastly, the simulated spectra indicate that it should be possible to probe the slower spectral diffusion of confined water compared to the bulk liquid by analysis of the 2D-IR spectra.« less
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