Abstract
Molecular-level knowledge of the thermodynamic, structural, and transport properties of water confined by interfaces and nanopores of various materials is crucial for quantitative understanding and prediction of many natural and technological processes, including carbon sequestration, water desalination, nuclear waste storage, cement chemistry, fuel cell technology, etc. Computational molecular modeling is capable to significantly complement the experimental investigations of such systems by providing invaluable atomic-scale information leading to improved understanding of the specific effects of the substrate structure and composition on the structure, dynamics and reactivity of interfacial and nano-confined aqueous solutions. This paper offers a brief overview of recent efforts to quantify some of these effects for individual H2O molecules and hydrated ions confined at the interfaces and in nanopores of several typical hydrophilic and hydrophobic materials. The first molecular layer of aqueous solution at all substrates is often highly ordered, indicating reduced translational and orientational mobility of the H2O molecules. This ordering cannot be simply described as “ice-like”, but rather resembles the behavior of supercooled water or amorphous ice, although with very significant substrate-specific variations.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Brown GE (2001) Surface science – How minerals react with water. Science 294:67–69
Sverjensky DA (2006) Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions. Geochim Cosmochim Acta 70:2427–2453
Brown GE, Calas G (2012) Mineral-aqueous solution interfaces and their impact on the environment. Geochem Perspect 1(4–5):483–742
Fenter P, Sturchio NC (2004) Mineral-water interfacial structures revealed by synchrotron X-ray scattering. Prog Surf Sci 77:171–258
Wenk H-R (ed) (2006) Neutron scattering in earth sciences. Rev Miner Geochem 63:1–471
Shen YR, Ostroverkhov V (2006) Sum-frequency vibrational spectroscopy on water interfaces: polar orientation of water molecules at interfaces. Chem Rev 106:1140–1154
Cole DR, Mamontov E, Rother G (2009) Structure and dynamics of fluids in microporous and mesoporous earth and engineered materials. In: Liang L, Rinaldi R, Schober H (eds) Neutron applications in earth, energy and environmental sciences. Springer, New York
Arbogast T (ed) (2007) Computational needs for the subsurface sciences. Workshop report. U.S. DOE Office of Science, Washington D.C., April 2007, 291pp
Frenkel D, Smit B (2002) Understanding molecular simulation: from algorithms to applications, 2nd edn. Academic, San Diego
Cygan RT, Kubicki JD (eds) (2001) Molecular modeling theory and applications in the geosciences. Rev Miner Geochem 42:1–531
Kalinichev AG, Kirkpatrick RJ (2002) Molecular dynamics modeling of chloride binding to the surfaces of Ca hydroxide, hydrated Ca-aluminate and Ca-silicate phases. Chem Mater 14:3539–3549
Cygan RT, Liang J-J, Kalinichev AG (2004) Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field. J Phys Chem B 108:1255–1266
Rustad JR, Felmy AR (2005) The influence of edge sites on the development of surface charge on goethite nanoparticles: a molecular dynamics study. Geochim Cosmochim Acta 69:1405–1411
Tossell JA (2005) Theoretical study on the dimerization of Si(OH)4 in aqueous solution and its dependence on temperature and dielectric constant. Geochim Cosmochim Acta 69:283–291
Criscenti LJ, Kubicki JD, Brantley SL (2006) Silicate glass and mineral dissolution: calculated reaction paths and activation energies for hydrolysis of a Q3 Si by H3O+ using ab initio methods. J Phys Chem A 110:198–206
Kerisit S, Rosso KM (2006) Computer simulation of electron transfer at hematite surfaces. Geochim Cosmochim Acta 70:1888–1903
Spagnoli D, Cooke DJ, Kerisit S, Parker SC (2006) Molecular dynamics simulations of the interaction between the surfaces of polar solids and aqueous solutions. J Mater Chem 16:1997–2006
Wang J, Kalinichev AG, Kirkpatrick RJ (2006) Effects of substrate structure and composition on the structure, dynamics and energetics of water on mineral surfaces: MD modeling study. Geochim Cosmochim Acta 70:562–582
Churakov SV (2007) Structure and dynamics of the water films confined between edges of pyrophyllite: a first principle study. Geochim Cosmochim Acta 71:1130–1144
Kalinichev AG, Wang J, Kirkpatrick RJ (2007) Molecular dynamics modeling of the structure, dynamics and energetics of mineral-water interfaces: application to cement materials. Cem Concr Res 37:337–347
Larentzos JP, Greathouse JA, Cygan RT (2007) An ab initio and classical molecular dynamics investigation of the structural and vibrational properties of talc and pyrophyllite. J Phys Chem C 111:12752–12759
de Leeuw NH, Cooper TG (2007) Surface simulation studies of the hydration of white rust Fe(OH)2, goethite α-FeO(OH) and hematite α-Fe2O3. Geochim Cosmochim Acta 71:1655–1673
Predota M, Cummings PT, Wesolowski DJ (2007) Electric double layer at the rutile (110) surface. 3. Inhomogeneous viscosity and diffusivity measurement by computer simulations. J Phys Chem C 111:3071–3079
Allen JP, Gren W, Molinari M, Arrouvel C, Maglia F, Parker SC (2009) Atomistic modelling of adsorption and segregation at inorganic solid interfaces. Mol Simul 35:584–608
Cygan RT, Greathouse JA, Heinz H, Kalinichev AG (2009) Molecular models and simulations of layered materials. J Mater Chem 19:2470–2481
Suter JL, Anderson RL, Greenwell HC, Coveney PV (2009) Recent advances in large-scale atomistic and coarse-grained molecular dynamics simulation of clay minerals. J Mater Chem 19:2482–2493
Wang J, Kalinichev AG, Kirkpatrick RJ (2009) Asymmetric hydrogen bonding and orientational ordering of water at hydrophobic and hydrophilic surfaces: a comparison of water/vapor, water/talc, and water/mica interfaces. J Phys Chem C 113:11077–11085
Argyris D, Cole DR, Striolo A (2010) Ion-specific effects under confinement: the role of interfacial water. ACS Nano 4:2035–2042
Bourg IC, Sposito G (2010) Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media. Environ Sci Technol 44:2085–2091
Malikova N, Dubois E, Marry V, Rotenberg B, Turq P (2010) Dynamics in clays – combining neutron scattering and microscopic simulation. Zeitschrift Phys Chem 224:153–181
Fenter P, Lee SS, Skelton AA, Cummings PT (2011) Direct and quantitative comparison of pixelated density profiles with high-resolution X-ray reflectivity data. J Synchrotron Radiat 18:257–265
Ferrage E, Sakharov BA, Michot LJ, Delville A, Bauer A, Lanson B, Grangeon S, Frapper G, Jimenez-Ruiz M, Cuello GJ (2011) Hydration properties and interlayer organization of water and ions in synthetic Na-smectite with tetrahedral layer charge. 2. Toward a precise coupling between molecular simulations and diffraction data. J Phys Chem C 115:1867–1881
Rotenberg B, Patel AJ, Chandler D (2011) Molecular explanation for why talc surfaces can be both hydrophilic and hydrophobic. J Am Chem Soc 133:20521–20527
Liu X, Lu X, Meijer EJ, Wang R, Zhou H (2012) Atomic-scale structures of interfaces between phyllosilicate edges and water. Geochim Cosmochim Acta 81:56–68
Tazi S, Rotenberg B, Salanne M, Sprik M, Sulpizi M (2012) Absolute acidity of clay edge sites from ab-initio simulations. Geochim Cosmochim Acta 94:1–11
Sahai N (2002) Is silica really an anomalous oxide? Surface acidity and aqueous hydrolysis revisited. Environ Sci Technol 36:445–452
Morrow CP, Yazaydin AO, Krishnan M, Bowers GM, Kalinichev AG, Kirkpatrick RJ (2013) Structure, energetics, and dynamics of smectite clay interlayer hydration: molecular dynamics and metadynamics investigation of Na-hectorite. J Phys Chem C 117:5172–5187
Duval Y, Mielczarski JA, Pokrovsky OS, Mielczarski E, Ehrhardt JJ (2002) Evidence of the existence of three types of species at the quartz-aqueous solution interface at pH 0-10: XPS surface group quantification and surface complexation modeling. J Phys Chem B 106:2937–2945
Ahn WY, Kalinichev AG, Clark MM (2008) Effects of background cations on the fouling of polyethersulfone membranes by natural organic matter: experimental and molecular modeling study. J Membr Sci 309:128–140
Wang JW, Kalinichev AG, Kirkpatrick RJ (2005) Structure and decompression melting of a novel, high-pressure nanoconfined 2-D ice. J Phys Chem B 109:14308–14313
Wang JW, Kalinichev AG, Kirkpatrick RJ (2004) Molecular modeling of the 10Å phase at subduction zone conditions. Earth Planet Sci Lett 222:517–527
Kalinichev AG (2001) Molecular simulations of liquid and supercritical water: thermodynamics, structure, and hydrogen bonding. Rev Mineral Geochem 42:83–129
Korb JP (2010) Multi-scales nuclear spin relaxation of liquids in porous media. Compt Rend Phys 11:192–203
Acknowledgments
This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences (grant number DE-FG02-08ER-15929) and by the industrial chair “Storage and Management of Nuclear Waste” at the Ecole des Mines de Nantes, funded by ANDRA, Areva, and EDF. The supercomputing resources of the NSF TeraGrid (grant number TG-EAR000002) and of the US DOE National Energy Research Scientific Computing Center (NERSC) were used for the simulations.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2014 Springer Science+Business Media Dordrecht
About this paper
Cite this paper
Kalinichev, A.G. (2014). Molecular Structure and Dynamics of Nano-Confined Water: Computer Simulations of Aqueous Species in Clay, Cement, and Polymer Membranes. In: Mercury, L., Tas, N., Zilberbrand, M. (eds) Transport and Reactivity of Solutions in Confined Hydrosystems. NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-7534-3_9
Download citation
DOI: https://doi.org/10.1007/978-94-007-7534-3_9
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-7533-6
Online ISBN: 978-94-007-7534-3
eBook Packages: Earth and Environmental ScienceEarth and Environmental Science (R0)