Water at interfaces Faraday Discussion

Water at interfaces Faraday Discussion 20 - 22 September 2023, London, UK

20 - 22 September 2023, London, UK Water at interfaces Faraday Discussion #FDWater

Book of Abstracts

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Introduction

Water at interfaces Faraday Discussion is organised by the Faraday Community for Physical Chemistry of the Royal Society of Chemistry This book contains abstracts of the posters presented at Water at interfaces Faraday Discussion. All abstracts are produced directly from typescripts supplied by authors. Copyright reserved.

Oral presentations and discussions All delegates at the meeting, not just speakers, have the opportunity to make comments, ask questions, or present complementary or contradictory measurements and calculations during the discussion. If it is relevant to the topic, you may give a 5-minute presentation of your own work during the discussion. These remarks are published alongside the papers in the final volume and are fully citable. If you would like to present slides during the discussion, please let the session chair know and load them onto the computer in the break before the start of the session. Faraday Discussion volume Copies of the discussion volume will be distributed approximately 6 months after the meeting. To expedite this, it is essential that summaries of contributions to the discussion are received no later than Friday 29 September 2023 for questions and comments and Friday 13 October for responses. Posters Posters have been numbered consecutively. The poster session will take place on Wednesday 20 September 2023 after the main sessions have ended. The posters will be available to view throughout the discussion during all refreshment breaks. During the dedicated poster session, authors should stand with their poster to discuss their research with other attendees.

Poster prize The Faraday Discussions poster prize will be awarded to the best student poster as judged by the committee.

Networking sessions There will be regular breaks throughout the meeting for socialising, networking and continuing discussions started during the scientific sessions.

Scientific Committee

Speakers

Mischa Bonn, (Chair) Max Planck Institute for Polymer Research, Germany

Rich Saykally, (Introductory Lecture) University of Berkeley, USA

Laura Fumagalli University of Manchester, UK Angelos Michaelides University of Cambridge, UK

Giulia Galli (Closing Lecture) University of Chicago, USA Ellen Backus University of Vienna, Austria Stephen Cox University of Cambridge, UK

Valeria Molinero University of Utah, USA

Karina Morgenstern University of Ruhr Bochum, Germany

Ulrike Diebold TU Wien, Austria

Yuki Nagata Max Planck Institute for Polymer Research, Germany

Ying Jiang Peking University, China

Nikita Kavokine Flatiron Institute, USA

Monica Olvera de la Cruz Northwestern University, USA

Adam Willard MIT, USA

Faraday Discussions Forum

www.rscweb.org/forums/fd/login.php In order to record the discussion at the meeting, which forms part of the final published volume, your name and e-mail address will be stored in the Faraday Forum. This information is used for the collection of questions and responses communicated during each session. After each question or comment you will receive an e-mail which contains some keywords to remind you what you asked, and your password information for the forum. The e-mail is not a full record of your question. You need to complete your question in full on the forum . The deadline for completing questions and comments is Friday 29 September 2023.

The question number in the e-mail keeps you a space on the forum. Use the forum to complete, review and expand on your question or comment. Figures and attachments can be uploaded to the forum. If you want to ask a question after the meeting, please e-mail faraday@rsc.org. Once we have received all questions and comments, responses will be invited by e-mail . These must also be completed on the forum . The deadline for completing responses is Friday 13 October 2023 Please note that when using the Forum to submit a question or reply, your name and registered e-mail address will be visible to other delegates registered for this Faraday Discussions meeting. Key points: • The e-mail is not a full record of your comment/question. • All comments and responses must be completed in full on the forum Deadlines: Questions and comments Friday 29 September 2023 Responses Friday 13 October 2023

Poster presentations

P01

Zwitterions modulate interfacial interactions across electrolyte solutions Kieran Agg University of Oxford, UK The role of water's hydrogen bonding network in interfacial acid-base chemistry on ice and other environmental surfaces Thorsten Bartels-Rausch Paul Scherrer Institut (PSI), Switzerland

P02

P03

A microscopic dipole model of water near an interface Ali Behjatian University of Oxford, UK Studies of water evaporation with raman thermometry Franky Bernal UC Berkeley, USA Classical quantum friction at water-carbon interfaces Anna Bui University of Cambridge, UK

P04

P06

P07

Water at the electrode-electolyte interface Andrew Burley University of Aberdeen, UK

P08

Ab initio investigations of the interaction of feldspar microcline with water Andrea Conti TU Wien, Austria Quantum feedback at the solid-liquid interface: flow-induced electronic current and its negative contribution to friction Baptiste Coquinot LPENS, PSL University, France How the pH of aqueous droplets and its size dependence are controlled by the air-water interface acidity Miguel de la Puente Ecole normale supérieure, France

P09

P10

P11

Depth-resolved SFG/DFG spectroscopy of charged aqueous interfaces Alvaro Diaz Duque Fritz Haber Institut, Germany Just how anisotropic is the air-water interface? Using depth-resolved SFG/DFG spectroscopy to determine its structure and thickness Alexander Fellows Fritz Haber Institut, Germany

P12

P13

Imaging feldspar microcline and the first stages of ice nucleation at the atomic scale

Giada Franceschi TU Wien, Austria

P14

Confined water in nanoporous silicas and organosilicas Michael Froeba University of Hamburg, Germany Influence of surfactants on the surface propensity of ions at the ocean-air interface Shirin Gholami Fritz-Haber-Institute der Max-Planck-Gesellschaft, Germany Interfacial H 2 O reactivity in bipolar membrane junctions Carlos Gomez Rodellar Fritz-Haber Institut of the Max-Planck Society, Germany The dramatic effect of water structure on hydration forces and the electrical double layer Jonathan Hedley Imperial College London, UK Applying a hybrid solvation model for simulating electrified Pt(111) and Ag(111) water interface Jack Hinsch Griffith University, Australia Electro-freezing of super-cooled water as a chemical process Leah Javitt Weizmann Institute, Israel

P15

P16

P17

P18

P19

P20

A combined first principles and experimental study of super-concentrated aqueous solutions of KOH Huang Jiajia The Hong Kong University of Science and Technology, China

P21

Fluidity of water in subnanometric confinement Di Jin Weizmann Institute of Science, Israel

P22

Ab initio reaction networks of carbon dioxide in supercritical water: bulk and nanoconfinement studies Chu Li The Hong Kong University of Science and Technology, Hong Kong Mass screening for nucleation agents for sodium acetate trihydrate and their relevance for heat batteries Jinjie Li University College London, UK Moving forward towards in-situ proton conduction dynamics in an operating fuel cell Sourav Maiti STFC, Rutherford Appleton Laboratory, UK

P23

P24

P25

Roles of interfacial water in carbon mineralisation Shurui Miao University of Oxford, UK

P26

Tailoring the interfacial water structure by electrolyte engineering for selective electrocatalytic reduction of carbon dioxide Nandita Mohandas Tata Institute of Fundamental Research India, India Neural-network based molecular dynamics simulation of the Fe$_3$O$_4$(001)-water interface Pablo Montero de Hijes University of Vienna, Austria Solvation shell water around gold nanoparticles of varying sizes studied by raman and infrared spectroscopy Taritra Mukherjee Max-Planck-Institut für Eisenforschung GmbH, Germany Quantification of the water-mediated interaction varying with solute size Hidefumi Naito Okayama University, Japan

P27

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P30

Trace ion concentration polarization near water-permeable salt-rejecting membranes Oded Nir Ben Gurion University of the Negev, Israel How good is DFT for ions in water? Machine-learning assisted benchmarks of the structure of aqueous electrolytes Niamh O'Neill University of Cambridge, UK Cholesterol modulates the hydration properties of model cell membranes in a lipid dependent manner Hanna Orlikowska-Rzeznik Poznan University of Technology, Poland Hydrophobic hydration: water-water structure around adamantane Luis Carlos Pardo Polytechnich University of Catalonia, Spain Investigating adsorption to soft-matter interfaces with second harmonic scattering Erika Riffe University of California, Berkeley, USA Surface tension measurement of pure water in its pure vapour Paul Ryan Technical University of Vienna, Austria Interfacial H 2 O reactivity during electrochemical NH 3 oxidation Francisco Jose Sarabia Gambin Fritz-Haber Institute of the Max-Planck Society, Germany Air/water interfaces in microdroplets control molecular de-aggregation Jenifer Shantha Kumar Indian Institute of Technology Madras, India Towards modeling laser-induced homogeneous ice nucleation from first principles Margarita Shepelenko Weizmann Institute of Science, Israel Dielectric properties of liquids confined in atomically thin nanochannels Mordjann Souilamas University of Manchester, UK

P31

P33

P34

P35

P36

P37

P38

P39

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P41

Temperature and pressure dependences of the solvation properties of alcohols in water Aoi Taira Okayama University, Japan Non Linear Ionic transport inside nanoslits: effect of the confinement on the correlations between electrolytes Damien Toquer LPENS/ENS/PSL, France Probing interfacial structure and electrostatic interactions in mixed surfactant systems using HD VSFG spectroscopy Aswathi Vilangottunjalil AMOLF Netherlands, Netherlands

P42

P43

P44

The role of interfacial water in inter-particle interactions Rowan Walker-Gibbons University of Oxford, UK

P45

Water sorption in the interface of salt mixture Shaoheng Wang University of Hamburg, Germany

P46

Interfacial water generates a long-ranged force between objects in solution Sida Wang Univeristy of Oxford, UK The impact of Ni and Cu dopants on water dissociation process at the nanoscale zero-valent iron-water interface Jessica White Griffith University, Australia Solvation free energies of molecules and ions: a first principles study Junting Yu The Hong Kong University of Science and Technology, Hong Kong Accurate refractive index measurements in nanoconfined spaces Peng Zhang King Abdullah University of Science and Technology, Saudi Arabia

P48

P49

P50

Zwitterions modulate interfacial interactions across electrolyte solutions Kieran Agg and Susan Perkin University of Oxford, UK Cellular functionality relies on the ability to maintain structure and function of biological macromolecules such as proteins, key to which is the surrounding chemical environment: the cytosol. Cytosol composition not only dictates the osmotic balance of cells with their surroundings, but also determines the range and nature of inter-protein interactions within the cell 1 . While the role of ionic solutes in destabilising proteins is well known, as illustrated by the Hofmeister series, the role that zwitterionic “osmolytes” play in these interactions is less clear. Here we will present a study of surface force measurements across model cytosol solutions, some of which have been recently reported 2 . These aqueous solutions containing pure zwitterion and salt-zwitterion mixtures reveal that common osmolytes such as trimethyl glycine and proline act to influence the interaction potential between charged mica sheets, including by enhancing the strength and range of electrostatic repulsion, disrupting water structure and forming molecular layers at charged interfaces. This multifaceted nature of zwitterionic osmolytes may be significant in how these molecules impart stability and balance in the cellular environment. References 1. Wennerström, H., Vallina Estrada, E., Danielsson, J.& Oliveberg, M. (2020). Colloidal stability of the living cell. Proc. Natl. Acad. Sci. , 117 (19), 10113–10121. 2. Hallett, J. E., Agg, K. J.& Perkin, S. (2023). Zwitterions fine-tune interactions in electrolyte solutions. Proc. Natl. Acad. Sci. , 120 (8),

P01

The role of water's hydrogen bonding network in interfacial acid- base chemistry on ice and other environmental surfaces Thorsten Bartels-Rausch Paul Scherrer Institut (PSI), Switzerland Cloud formation, atmospheric chemistry, and human health are influenced by multiphase chemistry at the air-substrate interface of atmospheric particles and ground surfaces 1 . All of these impacts are affected by acidity 2 . A conceptional understanding of interfacial acid-base character has not yet been reached 3 . Using X-ray photoemission spectroscopy at near ambient pressure, we have suggested that the dissociation of acids adsorbed to ice is governed by the availability and mobility of water molecules to stabilize the dissociated ions and that the degree of dissociation at the air-ice interface differs from that predicted based on dissociation behavior in aqueous bulk solutions 4,5 . Ice and snow host chemistry of relevance for the atmosphere and are of importance in cold regions of the Earth 6 . Here, we present additional results of fundamental studies on the structure of the hydrogen bonding network of interfacial water and the dissociation of acidic trace gases upon adsorption. We show a wider temperature range of the acid-base interfacial chemistry at -50°C and -20°C addressing the impact of the increased liquid-like character of ice at the air-ice interface at temperatures approaching the melting point. This increased flexibility of water molecules at the air-ice interface has also been called the pre-melting or quasi-liquid layer. By comparing the interfacial dissociation of HCl, HNO3, and acetic acid gives insights into the role of the acidic strength on the interfacial dissociation. Taken together, the data indicate a dominating role of the water availability on dissociation rather than the acidic strength or its temperature trend. We discuss how the limited availability of water may also be applied to other interfaces to explain the dissociation of acidic adsorbates there. References 1. Pöschl, U. and M. Shiraiwa, Chemical Reviews, 10.1021/cr500487s (2015) 2. Angle, K.J., D.R. Crocker, R.M.C. Simpson, K.J. Mayer, L.A. Garofalo, A.N. Moore, S.L. Mora Garcia, V.W. Or, S. Srinivasan, M. Farhan, J.S. Sauer, C. Lee, M.A. Pothier, D.K. Farmer, T.R. Martz, T.H. Bertram, C.D. Cappa, K.A. Prather, and V.H. Grassian, Proc Natl Acad Sci U S A, 10.1073/pnas.2018397118 (2021) 3. Saykally, R.J., Nature Chemistry, 10.1038/nchem.1556 (2013) 4. Kong, X., A. Waldner, F. Orlando, L. Artiglia, T. Huthwelker, M. Ammann, and T. Bartels-Rausch, J. Phys. Chem. Lett., 10.1021/acs.jpclett.7b01573 (2017) 5. Bartels-Rausch, T., F. Orlando, X. Kong, L. Artiglia, and M. Ammann, ACS Earth and Space Chemistry, 10.1021/ acsearthspacechem.7b00077 (2017) 6. Thomas, J.L., J. Stutz, M.M. Frey, T. Bartels-Rausch, K. Altieri, F. Baladima, J. Browse, M. Dall'Osto, L. Marelle, J. Mouginot, G.M. Jennifer, D. Nomura, K.A. Pratt, M.D. Willis, P. Zieger, J. Abbatt, T.A. Douglas, M.C. Facchini, J. France, A.E. Jones, K. Kim, P.A. Matrai, V.F. McNeill, A. Saiz-Lopez, P. Shepson, N. Steiner, K.S. Law, S.R. Arnold, B. Delille, J. Schmale, J.E. Sonke, A. Dommergue, D. Voisin, M.L. Melamed, and J. Gier, Elementa-Science of the Anthropocene, 10.1525/ elementa.396 (2019)

P02

A microscopic dipole model of water near an interface Ali Behjatian, Madhavi Krishnan Physical & Theoretical Chemistry Laboratory, University of Oxford, UK

Recent studies have shown that the anisotropic orientation of water molecules at interfaces in solution plays an important role in the anomalous experimentally observed phenomenon of attraction between like-charged colloidal particles in solutions 1-3 . Molecular dynamics (MD) simulations reveal that the orientation of water molecules at an interface significantly differs from bulk behaviour due to frustration at a discontinuity created by two different phases. Due to this symmetry-breaking effect of an interface, in general, the orientation of the water molecules near a charged interface can be anisotropic. These effects are not included in continuum electrostatics descriptions of interparticle interactions such as Poisson-Boltzmann (PB) theory that treat water as a featureless continuum. However, we have previously shown that in the calculation of the total interaction free energy between particles, a superposition of the PB electrostatic free energy, and an interfacial free energy due to water inferred from MD simulations does remarkably well in capturing various experimental trends 1-3 . While MD simulations provide detailed information on the molecular arrangement of water molecules at interfaces, an analytical model capturing the same behaviour would enable us to construct a self-consistent theoretical framework to describe interactions of macroscopic objects such as colloidal particles and polyelectrolytes. To this end, we present a statistical model that views water as an ensemble of noninteracting point-dipoles near a surface. We assume that the net molecular orientation near the interface is determined by the interplay of two types of potential energies: i) the electrostatic energy of dipoles in the electric field due to the charged particle, and ii) an additional short range symmetry breaking potential energy, which is non-zero within a shell of finite thickness in the vicinity of the interface. We incorporate this feature in a microscopic dipole description of the electric double layer system at an interface, and aim to show that by minimising the total free energy of the system, this behaviour of interfacial water can be explicitly and self-consistently implemented into the framework of a modified PB theory. Such a self-consistent model would be expected to improve upon the earlier superposition approach, and potentially enhance agreement of the model with experiments. Since virtually all biomolecules and colloidal particles in solution carry electrically charged groups, a molecular-level mean-field model of interparticle interactions would carry significant relevance in describing the profound effects of interfacial water in a wide range of particulate and molecular contexts.

A schematic representation of microscopic dipoles at a charged surface interacting with the electric field, and a symmetry breaking potential, u(x), close to the interface. References 1. Kubincová, A.; Hü nenberger, P. H.; Krishnan, M. J. Chem. Phys. 2020, 152, 104713.

2. Behjatian, A.; Walker-Gibbons, R.; Schekochihin, A. A.; Krishnan, M. Langmuir 2022, 38, 786. 3. Wang, S.; Walker-Gibbons, R.; Watkins, B.; Flynn, M.; Krishnan, M. arXiv:2212.12894.

P03

Studies of water evaporation with raman thermometry Franky Bernal 1,2 , Tony Rizzuto 3 and Richard Saykally 1,2 1 Department of Chemistry, University of California, USA, 2 Chemical Sciences Division, Lawrence Berkeley National Lab, USA, 3 Department of Chemistry, Elon University, USA A complete mechanistic description of water evaporation and condensation, inverse processes that govern a myriad of atmospheric phenomena, remains incomplete in modern science. Several groups have studied neat water in efforts to extract an evaporation coefficient, a parameter crucial in describing the kinetics of evaporation. Over the last few decades, the evaporation coefficient (γ) has been reported over the range 0.001 – 1. 1 The large dispersion in these measurements highlights the challenges associated with an accurate measurement of this quantity and the theory used to describe it. Our group has developed an experimental technique employing Raman Thermometry on liquid microjets in vacuum to determine the temperature of spherical microdroplets as they evaporate in a condensation-free environment. We previously reported γ for H 2 O and D 2 O as 0.62 +/- 0.09 2,3 , and found minimal change with added solutes such as ammonium sulfate and acetic acid. 4,5 However, Rizzuto et al recently found HCl solution concentration to have a significant impact on γ 6 . We are expanding these studies to other strong acids such as HBr and H 2 SO 4 , quantifying their effects on γ. Using a simple evaporation model based on the Hertz-Knudsen equation, we compare the extracted γ values of these acidic solutions to that of neat water. References 1. Marek, R.; Straub, J. Analysis of the Evaporation Coefficient and the Condensation Coefficient of Water. J. Heat Mass Transf. 2001 , 44 (1), 39–53. 2. Smith, J. D.; Cappa, C. D.; Drisdell, W. S.; Cohen, R. C.; Saykally, R. J. Raman Thermometry Measurements of Free Evaporation from Liquid Water Droplets. Am.Chem. Soc . 2006 , 128 , 12892−12898. 3. Drisdell, W. S.; Cappa, C. D.; Smith, J. D.; Saykally, R. J.; Cohen, R. C. Determination of the Evaporation Coefficient of D2O. Chem. Phys. Discuss . 2008 , 8, 8565−8583. 4. Duffey, K. C.; Shih, O.; Wong, N. L.; Drisdell, W. S.; Saykally, R. J.; Cohen, R. C. Evaporation Kinetics of Aqueous Acetic Acid Droplets: Effects of Soluble Organic Aerosol Components on the Mechanism of Water Evaporation. Chem. Chem. Phys . 2013 , 15 , 11634−11639. 5. Drisdell, W. S.; Saykally, R. J.; Cohen, R. C. On the Evaporation of Ammonium Sulfate Solution. Natl. Acad. Sci. U. S. A. 2009 , 106, 18897−18901. 6. Rizzuto, A. M.; Cheng, E. S.; Lam, R. K.; Saykally, R. J. Surprising Effects of Hydrochloric Acid on the Water Evaporation Coefficient Observed by Raman Thermometry. Phys. Chem. C 2017 , 121 (8), 4420–4425.

P04

Classical quantum friction at water-carbon interfaces Anna T. Bui, Fabian L. Thiemann, Angelos Michaelides, Stephen J. Cox University of Cambridge, UK

Friction at water–carbon interfaces remains a major puzzle with theories and simulations unable to explain experimental trends in nanoscale waterflow. A recent theoretical framework─quantum friction (QF)─proposes to resolve these experimental observations by considering nonadiabatic coupling between dielectric fluctuations in water and graphitic surfaces 1 . Here, using a classical model that enables fine-tuning of the solid’s dielectric spectrum, we provide evidence from simulations in general support of QF 2 . In particular, as features in the solid’s dielectric spectrum begin to overlap with water’s librational and Debye modes, we find an increase in friction in line with that proposed by QF. At the microscopic level, we find that this contribution to friction manifests more distinctly in the dynamics of the solid’s charge density than that of water. Our findings suggest that experimental signatures of QF may be more pronounced in the solid’s response rather than liquid water’s. References 1. N. Kavokine, M. Bocquet, L. Bocquet: Fluctuation-induced quantum friction in nanoscale water flows, Nature, 602, 84-90 (2022) 2. A. T. Bui, F. L. Thiemann, A. Michaelides, S. J. Cox: Classical quantum friction at water–carbon interfaces, Nano Lett., 23, 580-587 (2023)

P06

Water at the electrode-electolyte interface Andrew Burley, Pavithra Gunaeskaran and Angel Cuesta School of Chemistry, University of Aberdeen, UK

Water plays a crucial role in determining the properties of the electric double layer in aqueous electrolytes. Despite this, its behaviour is poorly understood. Surface enhanced infrared absorption spectroscopy in the attenuated total reflection configuration (ATR-SEIRAS) is highly sensitive to species within a few nm of the electrode surface, thus, it is highly suited to probe the dynamics of interfacial water. Osawa and co-workers were the first to apply this technique to explore the interfacial region 1 . We have used ATR-SEIRAS to improve our understanding of the structure of interfacial water at the gold-electrolyte interface by examining the O-H stretching of HOD molecules in 0.1 M HClO 4 dissolved in a 25% H 2 O / 75% D 2 O mixture. Examination of the ν OH band of HOD diluted in D 2 O shows significant changes from potentials below the point of zero charge (pzc) to potentials more positive than the pzc. In particular, deconvolution resolves two distinct contributions at potentials negative to the pzc, whilst three are observed at potentials positive of the pzc. The high frequency of this third contribution to the O-H stretching mode of interfacial HOD – around 3580 cm -1 – indicates a distinct population of interfacial water which experiences significant disruption to its hydrogen bonding network above the pzc. The intensity of this band, and therefore this population of disrupted water, increases as the potential becomes more positive. As perchlorate is known to be a chaotrope, this band is attributed to the effect of this ion migrating into the double layer. The δ HOD band shows a stepwise increase in frequency at the pzc, appearing at 1440 cm -1 below the pzc and 1460 cm -1 at potentials more positive to the pzc. Unexpectedly, the ratio of the intensities of the ν OH to ν D2O band differs for interfacial water versus the bulk. This allows us to hypothesise that water molecules have a tendency to adopt an orientation at the interface with one of the O-H bonds perpendicular to the surface, pointing either to ( E < pzc) or away ( E > pzc) of the gold surface. References 1. K. Ataka, T Yotsuyanagi and M Osawa, J. Phys. Chem . 1996 , 100 , 10664-10672

P07

Ab initio investigations of the interaction of feldspar microcline with water Andrea Conti, Giada Franceschi, Luca Lezuo, Florian Mittendorfer, Michael Schmid and Ulrike Diebold Institute of Applied Physics, Technical University of Vienna, Austria Feldspar microcline (KAlSi 3 O 8 ) is a common mineral in Earth's crust and plays a crucial role as an ice nucleator in atmospheric processes. Understanding its interaction with water is essential for various scientific fields, including geology and climate science. We employed density functional theory (DFT) to investigate different terminations of the feldspar microcline (001) surface and their interactions with water molecules. The metaGGA r 2 SCAN-D3 exchange-correlation functional 1 has been used to obtain the relaxed structures and the adsorption energies of the water molecules. The calculations show that there is a large energy gain from the dissociation of the first water molecule per unit cell and that the reaction proceeds without a barrier. In addition, our results show that the energetically preferred surface termination depends on the environmental conditions, namely the chemical potential of water. We correlate the DFT models with atomic force microscopy (AFM) simulations using the Probe Particle Model 2 to make a comparison with the experimental data imaged in UHV. These simulations enable us to investigate the behaviour of a CuOx tip 3 interacting with the modelled feldspar microcline surfaces under different water coverages. References 1. Ehlert et al. , "r 2 SCAN-D4: Dispersion corrected meta-generalized gradient approximation for general chemical applications", J. Chem. Phys. 154 , 061101 (2021). 2. Hapala et al. , "Mechanism of high-resolution STM/AFM imaging with functionalized tips", Phys. Rev. B 90 , 085421 (2014). 3. Lammers et al. , "Benchmarking atomically defined AFM tips for chemical-selective imaging", Nanoscale 13 , 13617 (2021).

P08

Quantum feedback at the solid-liquid interface: flow-induced electronic current and its negative contribution to friction Baptiste Coquinot 1,2,3 ,Lydéric Bocquet 1 and Nikita Kavokine 2,3 1 Laboratoire de Physique de l’É cole Normale Supérieure, ENS, Université PSL, France, 2 Center for Computational Quantum Physics, Flatiron Institute, USA, 3 Department of Molecular Spectroscopy, Max Planck Institute for Polymer Research, Germany An electronic current driven through a conductor can induce a current in another conductor through the famous Coulomb drag effect. Similar phenomena have been reported at the interface between a moving fluid and a conductor, but their interpretation has remained elusive. Here, we develop a quantum- mechanical theory of the intertwined fluid and electronic flows, taking advantage of the nonequilibrium Keldysh framework. We predict that a globally neutral liquid can generate an electronic current in the solid wall along which it flows. This hydrodynamic Coulomb drag originates from both the Coulomb interactions between the liquid’s charge fluctuations and the solid’s charge carriers and the liquid-electron interaction mediated by the solid’s phonons. We derive explicitly the Coulomb drag current in terms of the solid’s electronic and phononic properties, as well as the liquid’s dielectric response, a result which quantitatively agrees with recent experiments at the liquid-graphene interface. Furthermore, we show that the current generation counteracts momentum transfer from the liquid to the solid, leading to a reduction of the hydrodynamic friction coefficient through a quantum feedback mechanism. Our results provide a roadmap for controlling nanoscale liquid flows at the quantum level and suggest strategies for designing materials with low hydrodynamic friction. This poster is a presentation of 1 . References 1. B. Coquinot, L. Bocquet and N. Kavokine, Phys. Rev. X, 2023, 13, 011019

P09

How the pH of aqueous droplets and its size dependence are controlled by the air-water interface acidity Miguel de la Puente and Damien Laage PASTEUR, Department of Chemistry, cole Normale Supérieure, PSL University, France The air-water interface exhibits a unique chemical reactivity that is completely different from that in the bulk and that is central to fields ranging from “on-droplet” catalysis to atmospheric chemistry. 1 One of the most fundamental properties altered by the air-water interface is acidity. However, defining and measuring acidity in micro-droplets is extremely challenging, since factors ranging from system size to spatial resolution can critically impact such measurements. 2 Recent innovative experiments 3,4 have reported a mapping of acidity within droplets, but the results remain contrasted and a molecular understanding of the interface impact on acidity is needed. Molecular dynamics (MD) simulations are a precious tool to obtain a molecular-level picture of acidity in interfacial systems. However, the computational cost of typical reactive simulations traditionally imposes a compromise either on the accuracy of the electronic structure descriptions or on the statistical sampling, which are both required to provide a quantitative measure of acidity. Here, we overcome these limitations by employing deep neural network potentials 5 trained to reproduce potential energy surfaces of hybrid DFT quality at a fraction of the computational cost, which we combine with path-integral MD to account for nuclear quantum effects. 6 We performed reactive simulations of the water self-dissociation equilibrium and calculated the hydronium and hydroxide self-ion stabilities near the air-water interface. We then combined these results with an analytical model to determine the pH and self-ion concentration profiles within nano- and micro-droplets and to assess the impact of system size and interfacial depth on these key quantities. References 1. M.F. Ruiz-López et al. , Nat. Rev. Chem. , 2020, 4, 459-475 2. M. de la Puente et al. , J. Am. Chem. Soc. , 2022, 144, 10524-10529 3. M. Li et al. , Chem. , 2023, 9, 1-11 4. K. Gong et al. , Proc. Nat. Acad. Sci. U.S.A ., 2023, 120, 20, e2219588120 5. H. Wang et al. , Comput. Phys. Commun. , 2018, 228, 178-184 6. M. Ceriotti et al. , Phys. Rev. Lett. , 2012, 109, 100604

P10

Depth-resolved SFG/DFG spectroscopy of charged aqueous interfaces Alvaro Diaz-Duque, Alexander Fellows, Martin Wolf, Martin Thämer Fritz Haber Institut der Max Planck Gesellschaft, Deutschland Charged aqueous interfaces are omnipresent in our world, being a crucial ingredient in both natural systems including our physiology, the atmosphere, or geological structures, as well as technical devices such as electrochemical cells. Because of this importance such interfaces have been subject to extensive theoretical and experimental studies with the goal to obtain a microscopic understanding of their nature. The presence of interfacial charges and the generated electric fields leads to the formation of substantial anisotropies over a relatively large length scale in the interfacial region. These anisotropies result in depth dependent variations in chemical and physical properties in the electrolyte such as gradients in chemical compositions, depth specific molecular structures and modified dynamics of the water network. Over the past century important advances have been made in experiment and theory yielding a detailed molecular picture on interfacial ion distributions or the evolution of the electric potential with depth (e.g. the Gouy-Chapman (GC) or Gouy-Chapman-Stern (GCS) models), however, much less is known about the depth-depended properties of the main constituent in such electrolyte systems, the water. In the majority of the commonly used models the water is treated as a homogeneous solvent although from the current knowledge that we have on the complexity of the water structure and dynamics it becomes clear that this assumption is too simplistic. In this contribution, we investigate the depth dependent water structure at charged interfaces experimentally using the recently developed depth resolved nonlinear vibrational spectroscopy (SFG/DFG method)(1). This method allows for the analysis of preferential molecular orientations and intermolecular forces and correlates this information with spatial coordinates orthogonal to the interface. By probing both positive and negative charges, as well as their mixtures, and varying the sub-phase salt concentration, the depth-dependent structure of water in response to the residual (screened) field is extracted. The expected results from the GC and GCS models are then compared to the experimental observations to highlight any shortcomings. References 1. J. Phys. Chem. C 126, 26, 10818–10832 (2022).

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Just how anisotropic is the air-water interface? Using depth- resolved SFG/DFG spectroscopy to determine its structure and thickness Alexander P. Fellows 1 , Alvaro Diaz-Duque 1 , Louis Lehmann 2 , Roland Netz 2 , Martin Wolf 1 and Martin Thämer 1 1 Fritz Haber Institut der Max Planck Gesellschaft, Deutschland, 2 Freie Universität Berlin, Deutschland Liquid water possesses a well-studied three-dimensional bulk structure that is governed by its highly dynamic hydrogen bond network. Close to an interface this structure is greatly perturbed leading to the formation of an anisotropic interfacial layer with modified chemical and physical properties. These specialized properties of interfacial water govern various important processes in nature. Examples are many cellular functions in biology which are governed by the water properties at the interface to cell membranes as well as atmospheric aerosol chemistry where the properties of the air-water interface are considered crucial for the uptake mechanisms of gases as well as the kinetics of gas-phase reactions. In all of these examples not only is the specific characteristics of the first interfacial layer an essential parameter, but also the length-scale to which the structural perturbation extends towards the bulk. Despite the importance and an enormous amount of research our current understanding of interfacial water on a molecular level is still rather limited and often solely relies on results from molecular dynamics simulations. This is true even for the “simple” case of the pure air—water interface where important questions such as the thickness of the perturbed water layer and the depth dependent structural evolution remain largely unanswered. Recent simulations have suggested a surprisingly small thickness of the interfacial water layer on the sub-nanometer level; however, direct experimental evidence remains elusive. The work presented here shows a molecular level investigation of the air-water interface combining molecular dynamics simulations with experimental observations. The study focusses on revealing the depth dependent evolution of the water structure using the recently developed technique of depth resolved nonlinear vibrational spectroscopy (SFG/DFG method 1 ). By performing isotopic exchange experiments the obtained second-order spectra are decomposed into their resonant and non-resonant contributions which allows a direct comparison between experiment and results from simulations yielding a comprehensive molecular picture of the interfacial region. Based on these experiments the length-scale of the interfacial anisotropy decay is also determined providing the first direct experimental evidence of the thickness of the interfacial water layer at the boundary to air. References 1. J. Phys. Chem. C2022, 126, 26, 10818–10832

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Imaging feldspar microcline and the first stages of ice nucleation at the atomic scale Giada Franceschi, Luca Lezuo, Andrea Conti, Florian Mittendorfer, Michael Schmid and Ulrike Diebold Institute of Applied Physics, TU Wien, Austria Feldspar microcline (KAlSi 3 O 8 ) is a prominent mineral in the Earth’s crust and is present as dust particles in the atmosphere, where it nucleates ice with great efficiency. To unravel the greater ice-nucleating efficiency of microcline compared to other silicate dust particles, numerous studies have investigated the interaction of microcline with water. However, the relative importance of crystallographic orientations, lattice match between ice and microcline, cation composition, and defects for the ice-nucleating properties remain debated. Here, we present experimental surface studies of microcline and its interaction with water at low temperature. The surfaces were prepared by cleaving in ultrahigh vacuum (UHV) and analyzed with non-contact atomic force microscopy (nc-AFM) and x-ray photoelectron spectroscopy (XPS). The results provide direct views of the atomic- scale structure of microcline, exposes a hexagonal array of K + ions upon cleaving. Dosing water at 100K causes hydroxylation of the dry surface followed by the growth of a partially ordered water layer – possibly the onset of ice nucleation. The experimental results are interpreted with support from DFT calculations.

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Confined water in nanoporous silicas and organosilicas Michael Fröba 1,2 , B. Malfait 3 , A. Jani 3 , R. Lefort 3 , A. Moréac 3 , J.B. Mietner 1 , M. Busch 4 , P. Huber 5,6 , D. Morineau 3 1 Institute of Inorganic & Applied Chemistry, University of Hamburg, Germany, 2 The Hamburg Centre for Ultrafast Imaging, Germany, 3 Institute of Physics of Rennes, CNRS/University of Rennes, France, 4 Center for Integr. Multiscale Systems (CIMMS), Germany, 5 Institute for Materials and X-ray Physics, Germany, 6 Centre for X-Ray and Nano Science, Germany Water is undoubtedly the most important substance on earth. It is ubiquitous in nature and a necessary liquid for the emergence of life. In most frequent situations, water is found as spatially confined or in an interfacial state rather than forming a bulk phase. From a fundamental point of view, confining water at the nanoscale in prototypical porous solids has turned out to be particularly adequate in order to better understand the unusual behavior of interfacial water and ice. Here we present the some of the results of various studies dealing with the behavior of nanoconfined water in different nanoporous silicas and organosilicas with pore diameters between 2-4 nm 1,2 at different temperatures with respect to its dynamics (rotation, vibration and translation) and solidification/crystallization in the pores 3-5 . The used organosilicas barely used in water studies so far are very well suited to tune the water-pore surface interactions. The studies probe different time scales accompanied with different structural resolutions which allow a comprehensive view at the dynamics and structure of the water molecules and ice crystals. References 1. F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Silica-based mesoporous organic-inorganic hybrid materials, Angew. Chem. Int. Ed. 2006 , 45 , 3216-3251. 2. J.B. Mietner, F.J. Brieler, Y.J. Lee, M. Fröba, Properties of Water Confined in Periodic Mesoporous Organosilicas: Nanoimprinting the Local Structure, Angew. Chem. Int. Ed. 2017 , 56 , 12348-12351. 3. B. Malfait, A. Jani, J.B. Mietner, R. Lefort, P. Huber, M. Fröba, D. Morineau, Influence of Pore Surface Chemistry on the Rotational Dynamics of Nanoconfined Water, J. Phys. Chem. C 2021 , 125 , 16864-16874. 4. B. Malfait, A. Moréac, A. Jani, R. Lefort, P. Huber, M. Fröba, D. Morineau, Structure of Water at Hydrophilic and Hydrophobic Interfaces: Raman Spectroscopy of Water Confined in Periodic Mesoporous (Organo)Silicas, J. Phys. Chem. C 2022 , 126 , 3520-3531. 5. A. Jani, M. Busch, J.B. Mietner, J. Ollivier, M. Appel, B. Frick, J.-M. Zanotti, A. Ghoufi, P. Huber, M. Fröba, D. Morineau, Dynamics of water confined in mesopores with variable surface interaction, J. Chem. Phys. 2021 , 154 , 094505 (13 pp).

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Influence of surfactants on the surface propensity of ions at the ocean-air interface Shirin Gholami 1 , Tillmann Buttersack 1 , Florian Trinter 1,2 , Remi Dupuy 3 , Clemens Richter 1 , Jakob Filser 1 , Uwe Hergenhahn 1 , BerndWinter 1 , Karsten Reuter 1 , Hendrik Bluhm 1 1 Fritz Haber Institute of the Max Planck Society, Germany, 2 Institut fur Kernphysik, Goethe- Universität, Germany, 3 Sorbonne Université, France Liquid-vapor (especially aqueous-vapor) interfaces play a major role in atmospheric processes, for example in the interaction of the oceans or of aqueous aerosols with trace gases 1 . The contiguous aqueous-vapor interface is that of the oceans with air, covering more than 70% of Earth 2 . Studies have shown that the ocean-air interface is covered by a thin film of amphiphilic compounds, including surfactants 3 . This so-called sea surface microlayer significantly influences many processes with importance to the global ecosystem, such as the exchange of trace gases (e.g., CO 2 ) and heat, and the generation of aerosol particles [4-6]. The goal of our investigations is to elucidate the impacts of surfactants on the majority and minority ionic species in ocean water.We use X-ray photoelectron spectroscopy (XPS) coupled with a liquid microjet, which has been established as a powerful method for studies of surfactant molecules and dissolved ions, to study the liquid-vapor interface at the molecular level.The results of our investigations show the presence of positively and negatively charged surfactants can influence the propensity of different ions for the interface at ion concentrations found in seawater.Consequently, their availabilities for heterogeneous reactions at the ocean-air interface can be altered. References 1. Dupuy, R. et al. Phys. Chem. Chem. Phys. 24, 4796-4808 (2022).

2. Br ggemann, M. et al. Nat. Commun. 9 , 2101 (2018). 3. George, C. et al. Chem. Rev. 115, 4218–4258 (2015). 4. Wurl, O. et al. Prog. Oceanogr. 144, 15–24 (2016). 5. Adenaya, A. et al. Oceans 2, 752–771 (2021). 6. Winter, B. and Faubel, M. Chem. Rev. 106, 1176–1211 (2006).

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Interfacial H 2 O reactivity in bipolar membrane junctions Carlos Gomez Rodellar, Beatriz Roldan Cuenya, Sebastian Z. Öner Interface Science Department of the Fritz Haber Institute of the Max Planck Society, Germany H 2 O is omnipresent in electrochemistry, yet, its interfacial reactivity at metal oxide surfaces that exhibit a rich acid- base site chemistry is poorly understood. Here, we study interfacial water dissociation and formation (H 2 O <-> H + + OH - ) over metal(oxide) nanoparticle surfaces inside bipolar membrane (BPM) junctions. BPM junctions are comprised of a polymeric hydroxide ion conducting anion exchange layer (AEL), a metal (oxide) catalyst layer and a proton conducting cation exchange layer (CEL). Nafion is the prototypical example for a CEL. When applying a bias across the system, water can be dissociated (formed) inside the catalyst layer and hydroxide ions and protons are moving outward (inward). Despite the use of BPMs in industrial electrodialysis, the BPM catalyst activity is poorly understood. We are performing Tafel and Arrhenius analyses on pristine and TiO 2 -catalzed BPM junctions, and show that not only water dissociation can be catalyzed, as has been shown previously, 1,2 but also the reverse process of interfacial water formation. Studying the TiO 2 -loading dependence, we observe a transition of varying Ea(V) for pristine BPM junctions to a region of constant E a for TiO 2 -catalzed junctions. These results are paramount to understand the activity of pristine AEL and CEL sites and further show that additional, active metal oxide catalysts are maintained in their reversible state up to 100’s mA cm -2 . Conversely, for active catalysts with constant Ea, positive differential resistances are likely caused by a potential-dependent pre-exponential factor, A app (V), as we observe from Arrhenius analysis, and which might be indicative of electric field effects on interfacial water molecules. Further, we combine our experimental findings with Multiphysics simulations to develop an experimentally verifiable model about the BPM junction avoiding commonly made speculations. Last, we use our insights to demonstrate BPM fuel cells, that operate the hydrogen oxidation reaction in acidic and oxygen reduction reaction in alkaline conditions. References 1. S.Z. Oener, M. Foster, S.W. Boettcher, Accelerating Water Dissociation in Bipolar Membranes and Electrocatalysis, Science 369, 6507, 1099-1103 (2020), https://doi.org/10.1126/science.aaz1487 2. S. S. Mel’nikov, O. V. Shapovalova, N. V. Shel’deshov, V. I. Zabolotskii, Effect of d-metal hydroxides on water dissociation in bipolar membranes. Petrol. Chem. 51, 577–584 (2011). https://doi.org/10.1134/S0965544111070097

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The dramatic effect of water structure on hydration forces and the electrical double layer Jonathan Hedley 1 , Hélène Berthoumieux 2,3 , Alexei Kornyshev 1,4 1 Department of Chemistry, Imperial College London,UK, 2 Fachbereich Physik, Freie Universität Berlin, Germany, 3 Sorbonne Université, France, 4 Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, UK Overscreening oscillations in water structure play a significant role in water-mediated systems. This is shown in Israelachvili & Pashley’s hydration force experiments 1 alongside recent 3D-AFM experiments 2 . However, these oscillatory force profiles are only observed for atomically flat surfaces. Otherwise, monotonically decaying forces are observed 3 . Whilst oscillations being destroyed by surface roughness is conceptually intuitive, it is not exactly clear how water contributes to the behaviours above. We revisit this hydration force problem with an extended phenomenological Landau-Ginzburg approach describing nonlocal correlations in water, linking them with key features of the wavenumber-dependent dielectric function 4 . This theory predicts the observed oscillatory decay in hydration forces between flat surfaces, but these oscillations disappear with just a tiny surface roughness (corresponding to the size of a water molecule). Importantly, this explanation appears only possible assuming two polarisation modes in water, consistent with the behaviour of the response function. This resolves the “force- oscillation-non-oscillation" paradigm, which is a strong although indirect indication of the existence of these two modes. We also show by considering the same water structural effects that, even in dilute electrolytes, hydrated ions get trapped in potential wells created by the overscreening dielectric response of water to the charged surface. These oscillations are not new findings, having been observed in numerous simulations 5 . However, we establish the precise relation between the water electrostatic potential profile and density profiles of cations and anions - the ion distribution near the polarised interface preferentially follows the potential wells created by ‘resonance’ water- layering. Smearing of the interface results in a familiar Gouy-Chapman-Stern (GCS) picture. This result alone may explain why the GCS model works well for diluted solutions. Finally, we study how interfacial water-layering influences the double-layer capacitance and Parsons-Zobel plot gradients, resolving some recent puzzles 6 . References 1. Israelachvili, J. N., Pashley, R. M., Molecular layering of water at surfaces and origin of repulsive hydration forces. Nature, 306(5940) , 249–250. (1983). 2. Martin-Jimenez, D., Chacon, E., Tarazona, P.& Garcia, R., Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface. Nature Communications, 7(1) , 1–7. (2016). 3. Pashley, R. M., Hydration forces between mica surfaces in aqueous electrolyte solutions. Journal of Colloid and Interface Science, 80(1) , 153–162. (1981). 4. Hedley, J. G., Berthoumieux, H., Kornyshev, A. A., The dramatic effect of water structure on hydration forces and the electrical double layer. Journal of Physical Chemistry C (in press) , (2023). 5. Kornyshev, A. A., Spohr, E.& Vorotyntsev, M. A., Electrochemical Interfaces: At the Border Line& Schmickler, W., Electrical Double Layers: Theory and Simulations. In Encyclopedia of Electrochemistry (Vol. 1, pp. 133–161). Wiley-VCH. (2002). 6. Ojha, K., Arulmozhi, N., Aranzales, D.& Koper, M. T. M. Double Layer at the Pt(111)–Aqueous Electrolyte Interface: Potential of Zero Charge and Anomalous Gouy–Chapman Screening. Angewandte Chemie International Edition, 59(2) , 711–715. (2020)

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