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Azide–water intermolecular coupling measured by two-color two-dimensional infrared spectroscopy


Borek, Joanna; Perakis, Fivos; Kläsi, Felix; Garrett-Roe, Sean; Hamm, Peter (2012). Azide–water intermolecular coupling measured by two-color two-dimensional infrared spectroscopy. Journal of Chemical Physics, 136(22):224503.

Abstract

We utilize two-color two-dimensional infrared spectroscopy to measure the intermolecular coupling between azide ions and their surrounding water molecules in order to gain information about the nature of hydrogen bonding of water to ions. Our findings indicate that the main spectral contribution to the intermolecular cross-peak comes from population transfer between the asymmetric stretch vibration of azide and the OD-stretch vibration of D2O. The azide-bound D2O bleach/stimulated emission signal, which is spectrally much narrower than its linear absorption spectrum, shows that the experiment is selective to solvation shell water molecules for population times up to ∼500 fs. The waters around the ion are present in an electrostatically better defined environment. Afterwards, ∼1 ps, the sample thermalizes and selectivity is lost. On the other hand, the excited state absorption signal of the azide-bound D2O is much broader. The asymmetry in spectral width between bleach/stimulated emission versus excited absorption has been observed in very much the same way for isotope-diluted ice Ih, where it has been attributed to the anharmonicity of the OD potential.

Abstract

We utilize two-color two-dimensional infrared spectroscopy to measure the intermolecular coupling between azide ions and their surrounding water molecules in order to gain information about the nature of hydrogen bonding of water to ions. Our findings indicate that the main spectral contribution to the intermolecular cross-peak comes from population transfer between the asymmetric stretch vibration of azide and the OD-stretch vibration of D2O. The azide-bound D2O bleach/stimulated emission signal, which is spectrally much narrower than its linear absorption spectrum, shows that the experiment is selective to solvation shell water molecules for population times up to ∼500 fs. The waters around the ion are present in an electrostatically better defined environment. Afterwards, ∼1 ps, the sample thermalizes and selectivity is lost. On the other hand, the excited state absorption signal of the azide-bound D2O is much broader. The asymmetry in spectral width between bleach/stimulated emission versus excited absorption has been observed in very much the same way for isotope-diluted ice Ih, where it has been attributed to the anharmonicity of the OD potential.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:June 2012
Deposited On:19 Feb 2013 15:51
Last Modified:07 Dec 2017 19:32
Publisher:American Institute of Physics
ISSN:0021-9606
Funders:Swiss National Science Foundation (SNF) through the National Center of Competence and Research (NCCR) in Molecular Ultrafast Science and Technology (MUST)
Additional Information:(C) 2012 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 136, 224503(2012), and may be found at http://jcp.aip.org/resource/1/jcpsa6/v136/i22/p224503_s1
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1063/1.4726407
Official URL:http://jcp.aip.org/resource/1/jcpsa6/v136/i22/p224503_s1

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