Abstract
In this chapter, we report the submolecular-resolution imaging of water molecules adsorbed on a Au-supported NaCl(001) film with STM and nc-AFM. In the STM experiments, we first decouple electronically the water molecule from the metal substrate by inserting an insulating NaCl layer and then employed the STM tip as a top gate to tune controllably the molecular density of states of water around the Fermi level (EF). These key steps enable the direct visualizing of frontier molecular orbitals of adsorbed water, which allows discriminating the orientation of the monomers, the H-bond directionality of the tetramers in real space and characterization of H-bonded water clusters and overlayers on NaCl(001) film. In addition, we also achieve the submolecular-resolution imaging of water nanoclusters on the NaCl(001) film by probing the high-order electrostatic force using a qPlus-based nc-AFM with a CO-terminated tip. The non-invasive AFM imaging technique may open a new avenue of studying the intrinsic structure and dynamics of ice or water on surfaces, ion hydration and biological water with atomic precision.
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References
Thiel PA, Madey TE (1987) The interaction of water with solid surfaces: fundamental aspects. Surf Sci Rep 7:211–385
Henderson MA (2002) The interaction of water with solid surfaces: fundamental aspects revisited. Surf Sci Rep 46:1–308
Verdaguer A, Sacha GM, Bluhm H, Salmeron M (2006) Molecular structure of water at interfaces: Wetting at the nanometer scale. Chem Rev 106:1478–1510
Hodgson A, Haq S (2009) Water adsorption and the wetting of metal surfaces. Surf Sci Rep 64:381–451
Zou Z, Ye J, Sayama K, Arakawa H (2001) Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst. Nature 414:625–627
Akiya N, Savage PE (2002) Roles of water for chemical reactions in high-temperature water. Chem Rev 102:2725–2750
Kudo A, Miseki Y (2009) Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev 38:253–278
Eisenberg DS, Kauzmann W (1969) The structure and properties of water. Clarendon P., Oxford
Gross L, Mohn F, Moll N, Liljeroth P, Meyer G (2009) The chemical structure of a molecule resolved by atomic force microscopy. Science 325:1110–1114
Albrecht F, Neu M, Quest C, Swart I, Repp J (2013) Formation and characterization of a molecule-metal-molecule bridge in real space. J Am Chem Soc 135:9200–9203
Zhang J et al (2013) Real-space identification of intermolecular bonding with atomic force microscopy. Science 342:611–614
Kawai S et al (2016) Van der Waals interactions and the limits of isolated atom models at interfaces. Nat Commun 7:11559
Hämäläinen SK et al (2014) Intermolecular contrast in atomic force microscopy images without intermolecular bonds. Phys Rev Lett 113:186102
Guo J et al (2014) Real-space imaging of interfacial water with submolecular resolution. Nat Mater 13:184–189
Peng JB et al (2018) Weakly perturbative imaging of interfacial water with submolecular resolution by atomic force microscopy. Nat Commun 9:112
Chen J et al (2014) An unconventional bilayer ice structure on a NaCl(001) film. Nat Commun 5:4056
Meng X et al (2015) Direct visualization of concerted proton tunnelling in a water nanocluster. Nat Phys 11:235–239
Horcas I et al (2007) WSXM: a software for scanning probe microscopy and a tool for nanotechnology. Rev Sci Instrum 78:013705
Kresse G, Hafner J (1993) Ab initio molecular dynamics for liquid metals. Phys Rev B 47:558–561
Kresse G, Furthmuller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186
Klimes J, Bowler DR, Michaelides A (2011) Van der Waals density functionals applied to solids. Phys Rev B 83:195131
Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758–1775
Henkelman G, Uberuaga BP, Jonsson H (2000) A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys 113:9901–9904
Hapala P et al (2014) Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys Rev B 90:085421
Hapala P, Temirov R, Tautz FS, Jelinek P (2014) Origin of high-resolution IETS-STM images of organic molecules with functionalized tips. Phys Rev Lett 113:226101
Hebenstreit W et al (1999) Atomic resolution by STM on ultra-thin films of alkali halides: experiment and local density calculations. Surf Sci 424:L321–L328
Michaelides A, Ranea VA, de Andres PL, King DA (2003) General model for water monomer adsorption on close-packed transition and noble metal surfaces. Phys Rev Lett 90:216102
Cabrera-Sanfelix P, Arnau A, Darling GR, Sanchez-Portal D (2006) Water adsorption and diffusion on NaCl(100). J Phys Chem B 110:24559–24564
Yang Y, Meng S, Wang EG (2006) Water adsorption on a NaCl (001) surface: a density functional theory study. Phys Rev B 74:245409
Repp J, Meyer G, Stojkovic SM, Gourdon A, Joachim C (2005) Molecules on insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals. Phys Rev Lett 94:026803
Ho W (2002) Single-molecule chemistry. J Chem Phys 117:11033–11061
Kumagai T (2015) Direct observation and control of hydrogen-bond dynamics using low-temperature scanning tunneling microscopy. Prog Surf Sci 90:239–291
Norskov JK (1990) Chemisorption on metal surfaces. Rep Prog Phys 53:1253–1295
Martinez JI, Abad E, Gonzalez C, Flores F, Ortega J (2012) Improvement of scanning tunneling microscopy resolution with H-sensitized tips. Phys Rev Lett 108:246102
Lawton TJ, Carrasco J, Baber AE, Michaelides A, Sykes ECH (2011) Visualization of hydrogen bonding and associated chirality in methanol hexamers. Phys Rev Lett 107:256101
Bjerrum N (1952) Structure and properties of ice. Science 115:385–390
Forster M, Raval R, Hodgson A, Carrasco J, Michaelides A (2011) c(2 × 2) Water-hydroxyl layer on Cu(110): a wetting layer stabilized by Bjerrum defects. Phys Rev Lett 106:046103
Shiotari A, Sugimoto Y (2017) Ultrahigh-resolution imaging of water networks by atomic force microscopy. Nat Commun 8:14313
Cabrera-Sanfelix P et al (2007) Spontaneous emergence of Cl− anions from NaCl(100) at low relative humidity. J Phys Chem C 111:8000–8004
Klimes J, Bowler DR, Michaelides A (2013) Understanding the role of ions and water molecules in the NaCl dissolution process. J Chem Phys 139:234702
Liu L-M, Laio A, Michaelides A (2011) Initial stages of salt crystal dissolution determined with ab initio molecular dynamics. Phys Chem Chem Phys 13:13162–13166
Algara-Siller G et al (2015) Square ice in graphene nanocapillaries. Nature 519:443–445
Bernal JD, Fowler RH (1933) A theory of water and ionic solution, with particular reference to hydrogen and hydroxyl ions. J Chem Phys 1:515–548
Xu K, Cao P, Heath JR (2010) Graphene visualizes the first water adlayers on mica at ambient conditions. Science 329:1188–1191
Fukuma T, Ueda Y, Yoshioka S, Asakawa H (2010) Atomic-scale distribution of water molecules at the mica-water interface visualized by three-dimensional scanning force microscopy. Phys Rev Lett 104:016101
Songen H et al (2018) Resolving point defects in the hydration structure of calcite (10.4) with three-dimensional atomic force microscopy. Phys Rev Lett 120:116101
Thurmer K, Nie S (2013) Formation of hexagonal and cubic ice during low-temperature growth. Proc Natl Acad Sci U S A 110:11757–11762
Gross L et al (2010) Organic structure determination using atomic-resolution scanning probe microscopy. Nat Chem 2:821–825
Moll N, Gross L, Mohn F, Curioni A, Meyer G (2010) The mechanisms underlying the enhanced resolution of atomic force microscopy with functionalized tips. New J Phys 12:125020
Hapala P et al (2016) Mapping the electrostatic force field of single molecules from high-resolution scanning probe images. Nat Commun 7:11560
Ellner M et al (2016) The electric field of CO tips and its relevance for atomic force microscopy. Nano Lett 16:1974–1980
Chiang C-l XuC, Han Z, Ho W (2014) Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe. Science 344:885–888
Guo J et al (2016) Nuclear quantum effects of hydrogen bonds probed by tip-enhanced inelastic electron tunneling. Science 352:321–325
Giessibl FJ (2001) A direct method to calculate tip-sample forces from frequency shifts in frequency-modulation atomic force microscopy. Appl Phys Lett 78:123–125
Ternes M, Lutz CP, Hirjibehedin CF, Giessibl FJ, Heinrich AJ (2008) The force needed to move an atom on a surface. Science 319:1066–1069
Sader JE, Jarvis SP (2004) Accurate formulas for interaction force and energy in frequency modulation force spectroscopy. Appl Phys Lett 84:1801–1803
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Guo, J. (2018). Submolecular-Resolution Imaging of Interfacial Water. In: High Resolution Imaging, Spectroscopy and Nuclear Quantum Effects of Interfacial Water. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-13-1663-0_3
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DOI: https://doi.org/10.1007/978-981-13-1663-0_3
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