2D IR spectroscopy of high-pressure phases of ice.
- Tran H Department of Chemistry, University of Zürich, Zürich, Switzerland.
- Cunha AV Zernike Institute for Advanced Materials, University of Groningen, Groningen, The Netherlands.
- Shephard JJ Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
- Shalit A Department of Chemistry, University of Zürich, Zürich, Switzerland.
- Hamm P Department of Chemistry, University of Zürich, Zürich, Switzerland.
- Jansen TLC Zernike Institute for Advanced Materials, University of Groningen, Groningen, The Netherlands.
- Salzmann CG Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
- 2017-10-17
Published in:
- The Journal of chemical physics. - 2017
English
We present experimental and simulated 2D IR spectra of some high-pressure forms of isotope-pure D2O ice and compare the results to those of ice Ih published previously [F. Perakis and P. Hamm, Phys. Chem. Chem. Phys. 14, 6250 (2012); L. Shi et al., ibid. 18, 3772 (2016)]. Ice II, ice V, and ice XIII have been chosen for this study, since this selection covers many aspects of the polymorphism of ice. That is, ice II is a hydrogen-ordered phase of ice, in contrast to ice Ih, while ice V and ice XIII are a hydrogen-disordered/ordered couple that shares essentially the same oxygen structure and hydrogen-bonded network. For the transmission 2D IR spectroscopy, a novel method had to be developed for the preparation of ultrathin films (1-2 μm) of high-pressure ices with good optical quality. We also simulated 2D IR spectra based on molecular dynamics simulations connected to a vibrational exciton picture. These simulations agree with the experimental results in a semi-quantitative manner for ice II, while the same approach failed for ice V and ice XIII. From the perspective of 2D IR spectroscopy, ice II appears to be more inhomogeneously broadened than ice Ih, despite its hydrogen-order, which we attribute to the fact that ice II is structurally more complex with four distinguishable hydrogen bonds that mix due to exciton coupling. Ice V and ice XIII, on the other hand, behave as expected with the hydrogen-disordered case (ice V) being more inhomogenously broadened. Furthermore, in all hydrogen-ordered forms (ice II and ice XIII), cross peaks could be identified in the anisotropic 2D IR spectrum, whose signs reveal the relative direction of the corresponding excitonic states.
- Language
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- English
- Open access status
- green
- Identifiers
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- DOI 10.1063/1.4993952
- PMID 29031263
- Persistent URL
- https://sonar.ch/global/documents/256120
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