Talewar, Sukhpreet Kaur; (2021) Probing Structure and Dynamics of Amorphous Ice with Small-Molecule Nanoprobes. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

Water (H2O) is omnipresent on the surface of the Earth, the atmosphere, in nature, and on various celestial bodies.1 The phase diagram of ice exhibits enormous complexity with a plethora of structures and at least two amorphous ices. 2, 3 One of these, low-density amorphous ice, is the most abundant solid in the Universe. Despite H2O’s significance, a full understanding of its role in physical processes remains elusive.4 H2O is capable of building complex hydrogen-bonded networks, and solvates hydrophobic/hydrophilic species.2 Carbon and H2O often coexist, forming interfaces in highly diverse environments.5, 6 This thesis focuses on the structure of H2O in the hydration shells of hydrophobes, tracking the structure and dynamics of vapour deposited amorphous ice with finely dispersed small-molecule nanoprobes. Detailed insights into the morphology of amorphous solid water (ASW)7 and evidence for the presence of three discernible desorption processes present in macroscopic films of amorphous ice have been demonstrated. They are attributed to gas desorption from open cracks, from the collapse of internal voids, and from matrix-isolated gas induced by the irreversible crystallisation of H2O to stacking disordered ice. 7 Due to adamantane (C10H16) being expelled from the amorphous ice matrix upon heating, a number of important insights were gained – the uncharted regime of small hydrophobes surrounded by a H2O network were detected. Neutron diffraction studies of C10H16/ASW employing structure refinement modelling identified a new type of cage structure, with 28 H2O molecules constructed from distorted five- and six-membered rings, named the 566 4 polyhedron. Beyond this phenomenon, unusual, yet strong orientation correlations of the H2O molecules were detected. Intriguingly, the closest O– H bonds were found to point towards the centre of mass of C10H16 – it is quite striking that such a non-polar solute induces intense orientation correlations in its hydration shells. H2O has been at the forefront of many breakthroughs and will continue to push boundaries, probing the chemistry and physics of ice research. 3 References 1. L. del Rosso, M. Celli, F. Grazzi, M. Catti, T. C. Hansen, A. D. Fortes and L. Ulivi, Nat. Mater., 2020, 19, 663-668. 2. C. G. Salzmann, P. G. Radaelli, B. Slater and J. L. Finney, Phys. Chem. Chem. Phys., 2011, 13, 18468-18480. 3. C. G. Salzmann, J. Chem. Phys., 2019, 150, 060901. Abstract 4 4. T. Loerting, K. Winkel, M. Seidl, M. Bauer, C. Mitterdorfer, P. H. Handle, C. G. Salzmann, E. Mayer, J. L. Finney and D. T. Bowron, Phys. Chem. Chem. Phys., 2011, 13, 8783-8794. 5. M. C. De Sanctis, F. Capaccioni, M. Ciarniello, G. Filacchione, M. Formisano, S. Mottola, A. Raponi, F. Tosi, D. Bockelée-Morvan, S. Erard, C. Leyrat, B. Schmitt, E. Ammannito, G. Arnold, M. A. Barucci, M. Combi, M. T. Capria, P. Cerroni, W. H. Ip, E. Kuehrt, T. B. McCord, E. Palomba, P. Beck, E. Quirico, V. T. The, G. Piccioni, G. Bellucci, M. Fulchignoni, R. Jaumann, K. Stephan, A. Longobardo, V. Mennella, A. Migliorini, J. Benkhoff, J. P. Bibring, A. Blanco, M. Blecka, R. Carlson, U. Carsenty, L. Colangeli, M. Combes, J. Crovisier, P. Drossart, T. Encrenaz, C. Federico, U. Fink, S. Fonti, P. Irwin, Y. Langevin, G. Magni, L. Moroz, V. Orofino, U. Schade, F. Taylor, D. Tiphene, G. P. Tozzi, N. Biver, L. Bonal, J. P. Combe, D. Despan, E. Flamini, S. Fornasier, A. Frigeri, D. Grassi, M. S. Gudipati, F. Mancarella, K. Markus, F. Merlin, R. Orosei, G. Rinaldi, M. Cartacci, A. Cicchetti, S. Giuppi, Y. Hello, F. Henry, S. Jacquinod, J. M. Reess, R. Noschese, R. Politi and G. Peter, Nature, 2015, 525, 500. 6. B. A. Buffett, Annu. Rev. Earth Planet Sci., 2000, 28, 477-507. 7. S. K. Talewar, S. O. Halukeerthi, R. Riedlaicher, J. J. Shephard, A. E. Clout, A. Rosu-Finsen, G. R. Williams, A. Langhoff, D. Johannsmann and C. G. Salzmann, J. Chem. Phys., 2019, 151, 134505.

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