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

Title: First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface

Abstract

Reactions in the mineral surface/reservoir fluid interface control many geochemical processes such as the dissolution and growth of minerals (Yanina and Rosso 2008), heterogeneous oxidation/reduction (Hochella 1990, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008), and inorganic respiration (Newman 2010). Key minerals involved in these processes are the transition metal oxides and oxyhydroxides (e.g., hematite, Fe2O3, and goethite, FeOOH)(Brown, Henrich et al. 1999, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008). To interpret and predict these processes, it is necessary to have a high level of understanding of the interactions between the formations containing these minerals and their reservoir fluids. However, these are complicated chemical events occurring under a wide range of T, P, and X conditions and the interpretation is complicated by the highly heterogeneous nature of natural environments (Hochella 1990, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008) and the electronic and structural complexity of the oxide materials involved(Cox 1992, Kotliar and Vollhardt 2004, Navrotsky, Mazeina et al. 2008). In addition, also because of the complexity of the minerals involved and the heterogeneous nature of natural systems, the direct observation of these reactions at the atomic level ismore » experimentally extremely difficult. Theoretical simulations will provide important support for analysis of the geochemistry of the mineral surface/fluid region as well as provide essential tools to extrapolate laboratory measurements to the field environment.« less

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1415096
Report Number(s):
PNNL-SA-130898
49177; 49691; KC0302060
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Book
Resource Relation:
Related Information: Molecular Modeling of Geochemical Reactions: An Introduction, 107-149
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Chen, Ying, Bylaska, Eric J., and Weare, John H. First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface. United States: N. p., 2016. Web. doi:10.1002/9781118845226.ch4.
Chen, Ying, Bylaska, Eric J., & Weare, John H. First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface. United States. https://doi.org/10.1002/9781118845226.ch4
Chen, Ying, Bylaska, Eric J., and Weare, John H. 2016. "First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface". United States. https://doi.org/10.1002/9781118845226.ch4.
@article{osti_1415096,
title = {First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface},
author = {Chen, Ying and Bylaska, Eric J. and Weare, John H.},
abstractNote = {Reactions in the mineral surface/reservoir fluid interface control many geochemical processes such as the dissolution and growth of minerals (Yanina and Rosso 2008), heterogeneous oxidation/reduction (Hochella 1990, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008), and inorganic respiration (Newman 2010). Key minerals involved in these processes are the transition metal oxides and oxyhydroxides (e.g., hematite, Fe2O3, and goethite, FeOOH)(Brown, Henrich et al. 1999, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008). To interpret and predict these processes, it is necessary to have a high level of understanding of the interactions between the formations containing these minerals and their reservoir fluids. However, these are complicated chemical events occurring under a wide range of T, P, and X conditions and the interpretation is complicated by the highly heterogeneous nature of natural environments (Hochella 1990, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008) and the electronic and structural complexity of the oxide materials involved(Cox 1992, Kotliar and Vollhardt 2004, Navrotsky, Mazeina et al. 2008). In addition, also because of the complexity of the minerals involved and the heterogeneous nature of natural systems, the direct observation of these reactions at the atomic level is experimentally extremely difficult. Theoretical simulations will provide important support for analysis of the geochemistry of the mineral surface/fluid region as well as provide essential tools to extrapolate laboratory measurements to the field environment.},
doi = {10.1002/9781118845226.ch4},
url = {https://www.osti.gov/biblio/1415096}, journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Aug 01 00:00:00 EDT 2016},
month = {Mon Aug 01 00:00:00 EDT 2016}
}

Book:
Other availability
Please see Document Availability for additional information on obtaining the full-text document. Library patrons may search WorldCat to identify libraries that hold this book.

Save / Share:

Works referenced in this record:

Projector augmented-wave method
journal, December 1994


The Projector-Augmented Plane Wave Method Applied to Molecular Bonding
journal, December 1999


Mineral–water interfacial structures revealed by synchrotron X-ray scattering
journal, January 2004


Determination of the α-Ai 2 O 3 (0001) Surface Relaxation and Termination by Measurements of Crystal Truncation Rods
journal, February 1998


Effect of the Environment on α Al 2 O 3 (0001) Surface Structures
journal, April 2000


Theoretical Study of Properties of Goethite (α-FeOOH) at Ambient and High-Pressure Conditions
journal, March 2012


Strongly Correlated Materials: Insights From Dynamical Mean-Field Theory
journal, March 2004


Low intensity conduction states in FeS 2 : implications for absorption, open-circuit voltage and surface recombination
journal, October 2013


Fe2+Sorption at the Fe Oxide-Water Interface: A Revised Conceptual Framework
book, September 2011


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Water Structure and Hydrogen Bonding at Goethite/Water Interfaces: Implications for Proton Affinities
journal, February 2012


Interfacial water structure on the (012) surface of hematite: Ordering and reactivity in comparison with corundum
journal, November 2007


Geoscience research for our energy future
journal, August 2008


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998


Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide Nanoparticles
journal, September 2012


First Principles Simulation of the Bonding, Vibrational, and Electronic Properties of the Hydration Shells of the High-Spin Fe 3+ Ion in Aqueous Solutions
journal, February 2010


Norm-Conserving Pseudopotentials
journal, November 1979


Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


Hybrid density functional theory band structure engineering in hematite
journal, June 2011


Large-Scale Plane-Wave-Based Density Functional Theory: Formalism, Parallelization, and Applications
book, July 2011


Density-functional theory and NiO photoemission spectra
journal, December 1993


Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


One-Electron Reduction Potentials from Chemical Structure Theory Calculations
book, September 2011


The electronic structure of hematite {001} surfaces; applications to the interpretation of STM images and heterogeneous surface reactions
journal, December 1996


Ionization of High-Density Deep Donor Defect States Explains the Low Photovoltage of Iron Pyrite Single Crystals
journal, November 2014


Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure
journal, December 2001


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Crystal structure and isothermal compression of Fe2O3, Cr2O3, and V2O3 to 50 kbars
journal, January 1980


On the performance of eleven DFT functionals in the description of the vibrational properties of aluminosilicates: Performance of Eleven DFT Functionals
journal, July 2009


Near-Quantitative Agreement of Model-Free DFT-MD Predictions with XAFS Observations of the Hydration Structure of Highly Charged Transition-Metal Ions
journal, September 2012


Molecular dynamics without effective potentials via the Car-Parrinello approach
journal, August 1990


Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Structure and dynamics of liquid water on rutile TiO 2 ( 110 )
journal, October 2010


Fe(II) adsorption on hematite (0001)
journal, August 2009


Influence of Magnetite Stoichiometry on Fe II Uptake and Nitrobenzene Reduction
journal, May 2009


A new approach to quantification of metamorphism using ultra-small and small angle neutron scattering
journal, December 2009


Perspective: Fifty years of density-functional theory in chemical physics
journal, May 2014


Modeling Water Adsorption on Rutile (110) Using van der Waals Density Functional and DFT+U Methods
journal, October 2013


Empirical bond-strength–bond-length curves for oxides
journal, May 1973


Computer simulation of electron transfer at hematite surfaces
journal, April 2006


Density-Functional Theory of the Electronic Structure of Molecules
journal, October 1995


Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory
journal, January 2012


UO 2 Oxidative Corrosion by Nonclassical Diffusion
journal, June 2015


Electronic structure of α-Al2O3: Ab initio simulations and comparison with experiment
journal, April 2007


Structure and reactivity of synthetic Co-substituted goethites
journal, April 2008


Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH
journal, March 2010


Hydrated goethite (α-FeOOH) (100) interface structure: Ordered water and surface functional groups
journal, April 2010


Generalized norm-conserving pseudopotentials
journal, August 1989


Perspective on density functional theory
journal, April 2012


Spectroscopic Evidence for Fe(II)−Fe(III) Electron Transfer at the Iron Oxide−Water Interface
journal, September 2004


Competing retention pathways of uranium upon reaction with Fe(II)
journal, October 2014


First-principles calculation of the structure and magnetic phases of hematite
journal, April 2004


Density functional theory study of the clean and hydrated hematite ( 1 1 ¯ 02 ) surfaces
journal, February 2007


Pseudopotential methods in condensed matter applications
journal, April 1989


Periodic density functional theory calculations of bulk and the (010) surface of goethite
journal, May 2008


An ab initio model of electron transport in hematite (α-Fe2O3) basal planes
journal, April 2003


Density Functionals with Broad Applicability in Chemistry
journal, February 2008


Alumina(0001)/Water Interface: Structural Properties and Infrared Spectra from First-Principles Molecular Dynamics Simulations
journal, April 2014


Importance of Counteranions on the Hydration Structure of the Curium Ion
journal, June 2013


SURFACE SCIENCE: How Minerals React with Water
journal, October 2001


First-principles prediction of redox potentials in transition-metal compounds with LDA + U
journal, December 2004


Recent Developments in the Methods and Applications of the Bond Valence Model
journal, December 2009


Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction
journal, March 2008


The Iron Oxides
book, July 2003


Probing Outer-Sphere Adsorption of Aqueous Metal Complexes at the Oxide-Water Interface with Resonant Anomalous X-Ray Reflectivity
journal, February 2005


Thermodynamics of ionization of D2O and D2PO 4 ?
journal, December 1978


Nanominerals, Mineral Nanoparticles, and Earth Systems
journal, March 2008


Electronic, structural, and magnetic effects of 3d transition metals in hematite
journal, June 2010


Molecular Dynamics Simulations of the Goethite-water Interface
journal, January 2003


Structure and reactivity of the hydrated hematite (0001) surface
journal, December 2004


Fe(II) Sorption on Hematite:  New Insights Based on Spectroscopic Measurements
journal, January 2007


Photoemission satellites and electronic structure of Fe 2 O 3
journal, November 1986


Calculations of the electronic structure of 3d transition metal dimers with projector augmented plane wave method
journal, September 2003


Structures and energies of AlOOH and FeOOH polymorphs from plane wave pseudopotential calculations
journal, March 2001


Surface diffraction study of the hydrated hematite surface
journal, January 2007


All-electron study of gradient corrections to the local-density functional in metallic systems
journal, February 1995


Density functional theory study of Fe(II) adsorption and oxidation on goethite surfaces
journal, April 2009


Surface Complexation Modeling
journal, March 1995


The morphology of α-Al2O3 and α-Fe2O3: The importance of surface relaxation
journal, February 1987


Weak interfacial water ordering on isostructural hematite and corundum (001) surfaces
journal, April 2011


Water structure at hematite–water interfaces
journal, April 2011


Structure of the (0001) surface of α-Al2O3 from first principles calculations
journal, April 1993


Physical surface-complexation models for sorption at the mineral–water interface
journal, August 1993


Density Functional Theory of Open-Shell Systems. The 3d-Series Transition-Metal Atoms and Their Cations
journal, November 2013


Synchrotron X-ray study of the electron density in α-Fe 2 O 3
journal, August 1994


Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999


Inhomogeneous Electron Gas
journal, November 1964


How precise are measurements of unit-cell dimensions from single crystals?
journal, August 2000


Phonon spectra from short non-thermally equilibrated molecular dynamics simulations
journal, March 1994


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


Computing vibrational spectra from ab initio molecular dynamics
journal, January 2013


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


A study of hyperfine interactions in the system (Fe 1-x Rh x ) 2 O 3 using the Mossbauer effect (Bonding parameters)
journal, October 1971


Is the Calcite–Water Interface Understood? Direct Comparisons of Molecular Dynamics Simulations with Specular X-ray Reflectivity Data
journal, February 2013


Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral
journal, January 2011


Interpreting nanoscale size-effects in aggregated Fe-oxide suspensions: Reaction of Fe(II) with Goethite
journal, March 2008


Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite
journal, April 2015


Comment on “Structure and dynamics of liquid water on rutile TiO 2 (110)”
journal, April 2012


Molecular statics calculations for iron oxide and oxyhydroxide minerals: Toward a flexible model of the reactive mineral-water interface
journal, May 1996


Influence of Magnetite Stoichiometry on U VI Reduction
journal, December 2011