skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping

Abstract

Dopants have the potential to locally modify water-olivine interactions, which can impact geological processes, such as weathering, CO 2 sequestration, and abiotic hydrocarbon generation. As a first step in understanding the role of dopants on the water structure and chemistry at water-olivine interfaces, water monomer adsorption on alkaline earth (AE) and transition metal (TM) doped forsterite(010) [Mg 2SiO 4(010)] surfaces was studied in this work using density functional theory (DFT). Dopants that occur in olivine minerals were considered and consisted of Ca, Sr, and Ba for the AE dopants and Cr, Mn, Fe, Co, and Ni for the TM dopants. The water molecule adsorbs on the olivine surface through a metal-water bond (Me–Ow) and a hydrogen bond with an adjacent surface lattice oxygen (Ox–Hw). A frontier orbital analysis reveals that the 1b 2, 3a 1, and 1b 1 (HOMO) of the water molecule are involved in the bonding. All of the TM dopants show strong net Me–Ow covalent bonding between 3a 1 and 1b 1 water orbitals and TM d states, while the AE dopants except for Mg 2SiO 4(010) show negligible Me–Ow covalent bonding. Both the AE and TM dopants show similar hydrogen bonding features involving both the 1bmore » 2 and 3a 1 orbitals. While the AE cations show an overall lower Me–Ow covalent interaction, the AE dopants have strong electrostatic interactions between the positive metal cation and the negatively charged water dipole. A bonding model incorporating a linear combination of the covalent Me–Ow bond, the Ox–Hw hydrogen bond, the electrostatic interaction between the dopant cation and the H 2O molecule, and the surface distortion energy is needed to capture the variation in the DFT adsorption energies on the olivine surfaces. The bonding analysis is able to identify the dominant contributions to water-dopant interactions and can serve as a basis for future studies of more realistic water-olivine interfaces.« less

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States)
  2. Southwest Petroleum Univ., Chengdu (People’s Republic of China)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Sloan Foundation
OSTI Identifier:
1610910
Grant/Contract Number:  
SC0006878
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Liu, Tingting, Luo, Wenjia, Cole, David R., and Asthagiri, Aravind. Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping. United States: N. p., 2019. Web. doi:10.1063/1.5058770.
Liu, Tingting, Luo, Wenjia, Cole, David R., & Asthagiri, Aravind. Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping. United States. doi:10.1063/1.5058770.
Liu, Tingting, Luo, Wenjia, Cole, David R., and Asthagiri, Aravind. Mon . "Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping". United States. doi:10.1063/1.5058770. https://www.osti.gov/servlets/purl/1610910.
@article{osti_1610910,
title = {Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping},
author = {Liu, Tingting and Luo, Wenjia and Cole, David R. and Asthagiri, Aravind},
abstractNote = {Dopants have the potential to locally modify water-olivine interactions, which can impact geological processes, such as weathering, CO2 sequestration, and abiotic hydrocarbon generation. As a first step in understanding the role of dopants on the water structure and chemistry at water-olivine interfaces, water monomer adsorption on alkaline earth (AE) and transition metal (TM) doped forsterite(010) [Mg2SiO4(010)] surfaces was studied in this work using density functional theory (DFT). Dopants that occur in olivine minerals were considered and consisted of Ca, Sr, and Ba for the AE dopants and Cr, Mn, Fe, Co, and Ni for the TM dopants. The water molecule adsorbs on the olivine surface through a metal-water bond (Me–Ow) and a hydrogen bond with an adjacent surface lattice oxygen (Ox–Hw). A frontier orbital analysis reveals that the 1b2, 3a1, and 1b1 (HOMO) of the water molecule are involved in the bonding. All of the TM dopants show strong net Me–Ow covalent bonding between 3a1 and 1b1 water orbitals and TM d states, while the AE dopants except for Mg2SiO4(010) show negligible Me–Ow covalent bonding. Both the AE and TM dopants show similar hydrogen bonding features involving both the 1b2 and 3a1 orbitals. While the AE cations show an overall lower Me–Ow covalent interaction, the AE dopants have strong electrostatic interactions between the positive metal cation and the negatively charged water dipole. A bonding model incorporating a linear combination of the covalent Me–Ow bond, the Ox–Hw hydrogen bond, the electrostatic interaction between the dopant cation and the H2O molecule, and the surface distortion energy is needed to capture the variation in the DFT adsorption energies on the olivine surfaces. The bonding analysis is able to identify the dominant contributions to water-dopant interactions and can serve as a basis for future studies of more realistic water-olivine interfaces.},
doi = {10.1063/1.5058770},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 150,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Laboratory Simulations of Abiotic Hydrocarbon Formation in Earth's Deep Subsurface
journal, January 2013


Josephinite: specimens from the earth's core? — a discussion
journal, July 1976


Perspective: A controversial benchmark system for water-oxide interfaces: H2O/TiO2(110)
journal, July 2017

  • Diebold, Ulrike
  • The Journal of Chemical Physics, Vol. 147, Issue 4
  • DOI: 10.1063/1.4996116

Chemical bonding of water to metal surfaces studied with core-level spectroscopies
journal, March 2010

  • Schiros, T.; Andersson, K. J.; Pettersson, L. G. M.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 177, Issue 2-3
  • DOI: 10.1016/j.elspec.2009.09.009

Performance of dispersion-corrected density functional theory for the interactions in ionic liquids
journal, January 2012

  • Grimme, Stefan; Hujo, Waldemar; Kirchner, Barbara
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 14
  • DOI: 10.1039/c2cp24096c

Implementation of empirical dispersion corrections to density functional theory for periodic systems
journal, June 2012

  • Reckien, Werner; Janetzko, Florian; Peintinger, Michael F.
  • Journal of Computational Chemistry, Vol. 33, Issue 25
  • DOI: 10.1002/jcc.23037

Coulombic Amino Group-Metal Bonding: Adsorption of Adenine on Cu(110)
journal, June 2005


Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements
journal, October 1994


A grid-based Bader analysis algorithm without lattice bias
journal, January 2009


Serpentinites, Hydrogen, and Life
journal, April 2013


How Does Water Bind to Metal Surfaces: Hydrogen Atoms Up or Hydrogen Atoms Down?
journal, August 2003


Insight from first principles into the nature of the bonding between water molecules and 4d metal surfaces
journal, January 2009

  • Carrasco, Javier; Michaelides, Angelos; Scheffler, Matthias
  • The Journal of Chemical Physics, Vol. 130, Issue 18
  • DOI: 10.1063/1.3125002

On the Stability of Sulfides, Oxides, and Native Metals in Serpentinite
journal, February 1985


Density Functional Theory Calculations of Hydrogen-Containing Defects in Forsterite, Periclase, and α-Quartz
journal, October 2001

  • de Leeuw, Nora H.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 40
  • DOI: 10.1021/jp0109978

Structures of twinned β-Sr2SiO4 and of α'-Sr1.9Ba0.1SiO4
journal, January 1983

  • Catti, M.; Gazzoni, G.; Ivaldi, G.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 39, Issue 1
  • DOI: 10.1107/s0108270183003492

Abiotic Synthesis of Organic Compounds in Deep-Sea Hydrothermal Environments
journal, February 2007

  • McCollom, Thomas M.; Seewald, Jeffrey S.
  • Chemical Reviews, Vol. 107, Issue 2
  • DOI: 10.1021/cr0503660

Structural Sensitivity in the Dissociation of Water on TiO 2 Single-Crystal Surfaces
journal, January 1996


Polar oxide surfaces
journal, July 2000


A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


The interaction of water with solid surfaces: fundamental aspects revisited
journal, May 2002


Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993

  • Dronskowski, Richard; Bloechl, Peter E.
  • The Journal of Physical Chemistry, Vol. 97, Issue 33
  • DOI: 10.1021/j100135a014

Anomalous high adsorption energy of H 2 O on fluorinated graphenes: a first principles study
journal, January 2014

  • Wang, Peng; Wang, Hongtao; Yang, Wei
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 38
  • DOI: 10.1039/c4cp01784f

Water at Interfaces
journal, April 2016


Improved Description of the Structure of Molecular and Layered Crystals: Ab Initio DFT Calculations with van der Waals Corrections
journal, November 2010

  • Bučko, Tomáš; Hafner, Jürgen; Lebègue, Sébastien
  • The Journal of Physical Chemistry A, Vol. 114, Issue 43
  • DOI: 10.1021/jp106469x

Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids
journal, September 2013

  • Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
  • Journal of Computational Chemistry, Vol. 34, Issue 29
  • DOI: 10.1002/jcc.23424

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Hydrocarbons in Hydrothermal Vent Fluids: The Role of Chromium-Bearing Catalysts
journal, May 2004


Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

A fossil, serpentinization-related hydrothermal vent, Ocean Drilling Program Leg 173, Site 1068 (Iberia Abyssal Plain): Some aspects of mineral and fluid chemistry
journal, July 2000

  • Beard, James S.; Hopkinson, Laurence
  • Journal of Geophysical Research: Solid Earth, Vol. 105, Issue B7
  • DOI: 10.1029/2000jb900073

Fe-Ni-Co-O-S Phase Relations in Peridotite-Seawater Interactions
journal, January 2009


Heterogeneous Catalysis on Metal Oxides
journal, November 2017


The β <-> α' phase transition of Sr 2 SiO 4 . I. Order–disorder in the structure of the α' form at 383 K
journal, December 1983

  • Catti, M.; Gazzoni, G.; Ivaldi, G.
  • Acta Crystallographica Section B Structural Science, Vol. 39, Issue 6
  • DOI: 10.1107/s0108768183003213

A molecular perspective of water at metal interfaces
journal, July 2012

  • Carrasco, Javier; Hodgson, Andrew; Michaelides, Angelos
  • Nature Materials, Vol. 11, Issue 8
  • DOI: 10.1038/nmat3354

Abiogenic Hydrocarbon Production at Lost City Hydrothermal Field
journal, February 2008


Initial water adsorption on hematite ( α -Fe 2 O 3 ) (0001): A DFT + U study
journal, March 2018

  • Wang, Richard B.; Hellman, Anders
  • The Journal of Chemical Physics, Vol. 148, Issue 9
  • DOI: 10.1063/1.5020358

Carbon Dioxide Sequestration A Solution to a Global Problem
journal, October 2008


Modelling the effect of water on the surface structure and stability of forsterite
journal, May 2000

  • de Leeuw, N. H.; Parker, S. C.; Catlow, C. R. A.
  • Physics and Chemistry of Minerals, Vol. 27, Issue 5
  • DOI: 10.1007/s002690050262

Adsorption, Desorption, and Displacement Kinetics of H 2 O and CO 2 on Forsterite, Mg 2 SiO 4 (011)
journal, October 2014

  • Smith, R. Scott; Li, Zhenjun; Dohnálek, Zdenek
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp504187y

LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding
journal, February 2016

  • Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
  • Journal of Computational Chemistry, Vol. 37, Issue 11
  • DOI: 10.1002/jcc.24300

Climate Change and CO2 Removal from the Atmosphere
journal, January 2014


Interaction between Olivine and Water Based on Density Functional Theory Calculations
journal, October 2013

  • Prigiobbe, Valentina; Suarez Negreira, Ana; Wilcox, Jennifer
  • The Journal of Physical Chemistry C, Vol. 117, Issue 41
  • DOI: 10.1021/jp403271e

Computer simulations of water interactions with low-coordinated forsterite surface sites: Implications for the origin of water in the inner solar system
journal, November 2010


Performance of Non-Local and Atom-Pairwise Dispersion Corrections to DFT for Structural Parameters of Molecules with Noncovalent Interactions
journal, October 2012

  • Hujo, Waldemar; Grimme, Stefan
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct300813c

Dissolution of basalts and peridotite in seawater, in the presence of ligands, and CO2: Implications for mineral sequestration of carbon dioxide
journal, October 2011

  • Wolff-Boenisch, Domenik; Wenau, Stefan; Gislason, Sigurdur R.
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 19
  • DOI: 10.1016/j.gca.2011.07.004

Ab initio study of the chemical states of water on Cr2O3(0001): From the isolated molecule to saturation coverage
journal, August 2009


Optimization methods for finding minimum energy paths
journal, April 2008

  • Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme
  • The Journal of Chemical Physics, Vol. 128, Issue 13
  • DOI: 10.1063/1.2841941

Permanent storage of carbon dioxide in geological reservoirs by mineral carbonation
journal, November 2009

  • Matter, Jürg M.; Kelemen, Peter B.
  • Nature Geoscience, Vol. 2, Issue 12
  • DOI: 10.1038/ngeo683

Mineral Carbonation of CO2
journal, October 2008


Hydrogen-Bond Relations for Surface OH Species
journal, January 2018

  • Kebede, Getachew G.; Mitev, Pavlin D.; Broqvist, Peter
  • The Journal of Physical Chemistry C, Vol. 122, Issue 9
  • DOI: 10.1021/acs.jpcc.7b10981

Structure and dynamics of forsterite–scCO2/H2O interfaces as a function of water content
journal, May 2012

  • Kerisit, Sebastien; Weare, John H.; Felmy, Andrew R.
  • Geochimica et Cosmochimica Acta, Vol. 84
  • DOI: 10.1016/j.gca.2012.01.038

Density functional theory with London dispersion corrections: Density functional theory with London dispersion corrections
journal, March 2011

  • Grimme, Stefan
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2
  • DOI: 10.1002/wcms.30

An ångström-sized window on the origin of water in the inner solar system: Atomistic simulation of adsorption of water on olivine
journal, August 2006


Improved grid-based algorithm for Bader charge allocation
journal, January 2007

  • Sanville, Edward; Kenny, Steven D.; Smith, Roger
  • Journal of Computational Chemistry, Vol. 28, Issue 5
  • DOI: 10.1002/jcc.20575

Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets
journal, June 2011

  • Deringer, Volker L.; Tchougréeff, Andrei L.; Dronskowski, Richard
  • The Journal of Physical Chemistry A, Vol. 115, Issue 21
  • DOI: 10.1021/jp202489s

Water and carbon dioxide adsorption at olivine surfaces
journal, November 2013


The role of van der Waals forces in water adsorption on metals
journal, January 2013

  • Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773901

Calorimetric study of the surface energy of forsterite
journal, December 2009


On the Importance of the Dispersion Energy for the Thermodynamic Stability of Molecules
journal, March 2011

  • Grimme, Stefan; Huenerbein, Robert; Ehrlich, Stephan
  • ChemPhysChem, Vol. 12, Issue 7
  • DOI: 10.1002/cphc.201100127

Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms
journal, January 1999

  • Brown, Gordon E.; Henrich, Victor E.; Casey, William H.
  • Chemical Reviews, Vol. 99, Issue 1
  • DOI: 10.1021/cr980011z

Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction
journal, May 1998

  • Alt, Jeffrey C.; Shanks, Wayne C.
  • Journal of Geophysical Research: Solid Earth, Vol. 103, Issue B5
  • DOI: 10.1029/98jb00576

Termination and hydration of forsteritic olivine (0 1 0) surface
journal, November 2014


Trends in water monomer adsorption and dissociation on flat insulating surfaces
journal, January 2011

  • Hu, Xiao Liang; Carrasco, Javier; Klimeš, Jiří
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 27
  • DOI: 10.1039/c1cp20846b