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.
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14 October 2017
Research Article|
October 10 2017
2D IR spectroscopy of high-pressure phases of ice
Halina Tran
;
Halina Tran
a)
1
Department of Chemistry, University of Zürich
, Zürich, Switzerland
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Ana V. Cunha;
Ana V. Cunha
a)
2
Zernike Institute for Advanced Materials, University of Groningen
, Groningen, The Netherlands
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Jacob J. Shephard;
Jacob J. Shephard
3
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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Andrey Shalit;
Andrey Shalit
1
Department of Chemistry, University of Zürich
, Zürich, Switzerland
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Peter Hamm
;
Peter Hamm
b)
1
Department of Chemistry, University of Zürich
, Zürich, Switzerland
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Thomas L. C. Jansen
;
Thomas L. C. Jansen
b)
2
Zernike Institute for Advanced Materials, University of Groningen
, Groningen, The Netherlands
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Christoph G. Salzmann
Christoph G. Salzmann
b)
3
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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a)
H. Tran and A. V. Cunha contributed equally to this work.
b)
Authors to whom correspondence should be addressed: peter.hamm@chem.uzh.ch, t.l.c.jansen@rug.nl, and c.salzmann@ucl.ac.uk
J. Chem. Phys. 147, 144501 (2017)
Article history
Received:
July 03 2017
Accepted:
August 30 2017
Citation
Halina Tran, Ana V. Cunha, Jacob J. Shephard, Andrey Shalit, Peter Hamm, Thomas L. C. Jansen, Christoph G. Salzmann; 2D IR spectroscopy of high-pressure phases of ice. J. Chem. Phys. 14 October 2017; 147 (14): 144501. https://doi.org/10.1063/1.4993952
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