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

Title: Supersaturated calcium carbonate solutions are classical

Abstract

We will present a description of nucleation phenomena in the condensed phase that takes into account non-ideal solution effects associated with cluster-cluster interaction. To do this we employ aggregation-volume bias Monte Carlo simulation, making the estimation of free-energy of large pre-critical clusters of sizes 10-20 tractable. We will compare and contrast empirical potential and electronic structure (e.g. Density functional theory) based descriptions of molecular interaction associated with the nucleation of CaCO 3, highlighting free-energy trends and qualitative differences in populations of pre-critical clusters as a function of supersaturation. The influence of how the precise local interaction influences the non-ideal solution behavior on the nucleation and growth processes will be highlighted. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ; ; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1492305
Report Number(s):
PNNL-SA-128147
Journal ID: ISSN 2375-2548
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English

Citation Formats

Henzler, Katja, Fetisov, Evgenii O., Galib, Mirza, Baer, Marcel D., Legg, Benjamin A., Borca, Camelia, Xto, Jacinta M., Pin, Sonia, Fulton, John L., Schenter, Gregory K., Govind, Niranjan, Siepmann, J. Ilja, Mundy, Christopher J., Huthwelker, Thomas, and De Yoreo, James J. Supersaturated calcium carbonate solutions are classical. United States: N. p., 2018. Web. doi:10.1126/sciadv.aao6283.
Henzler, Katja, Fetisov, Evgenii O., Galib, Mirza, Baer, Marcel D., Legg, Benjamin A., Borca, Camelia, Xto, Jacinta M., Pin, Sonia, Fulton, John L., Schenter, Gregory K., Govind, Niranjan, Siepmann, J. Ilja, Mundy, Christopher J., Huthwelker, Thomas, & De Yoreo, James J. Supersaturated calcium carbonate solutions are classical. United States. doi:10.1126/sciadv.aao6283.
Henzler, Katja, Fetisov, Evgenii O., Galib, Mirza, Baer, Marcel D., Legg, Benjamin A., Borca, Camelia, Xto, Jacinta M., Pin, Sonia, Fulton, John L., Schenter, Gregory K., Govind, Niranjan, Siepmann, J. Ilja, Mundy, Christopher J., Huthwelker, Thomas, and De Yoreo, James J. Mon . "Supersaturated calcium carbonate solutions are classical". United States. doi:10.1126/sciadv.aao6283.
@article{osti_1492305,
title = {Supersaturated calcium carbonate solutions are classical},
author = {Henzler, Katja and Fetisov, Evgenii O. and Galib, Mirza and Baer, Marcel D. and Legg, Benjamin A. and Borca, Camelia and Xto, Jacinta M. and Pin, Sonia and Fulton, John L. and Schenter, Gregory K. and Govind, Niranjan and Siepmann, J. Ilja and Mundy, Christopher J. and Huthwelker, Thomas and De Yoreo, James J.},
abstractNote = {We will present a description of nucleation phenomena in the condensed phase that takes into account non-ideal solution effects associated with cluster-cluster interaction. To do this we employ aggregation-volume bias Monte Carlo simulation, making the estimation of free-energy of large pre-critical clusters of sizes 10-20 tractable. We will compare and contrast empirical potential and electronic structure (e.g. Density functional theory) based descriptions of molecular interaction associated with the nucleation of CaCO3, highlighting free-energy trends and qualitative differences in populations of pre-critical clusters as a function of supersaturation. The influence of how the precise local interaction influences the non-ideal solution behavior on the nucleation and growth processes will be highlighted. This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.},
doi = {10.1126/sciadv.aao6283},
journal = {Science Advances},
issn = {2375-2548},
number = 1,
volume = 4,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


A Molecular Dynamics Study of the Early Stages of Calcium Carbonate Growth
journal, August 2009

  • Tribello, Gareth A.; Bruneval, Fabien; Liew, CheeChin
  • The Journal of Physical Chemistry B, Vol. 113, Issue 34
  • DOI: 10.1021/jp902606x

Amorphous Calcium Carbonate: Synthesis and Potential Intermediate in Biomineralization
journal, June 2004


Changes in the Silanol Protonation State Measured In Situ at the Silica–Aqueous Interface
journal, January 2012

  • Brown, Matthew A.; Huthwelker, Thomas; Beloqui Redondo, Amaia
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
  • DOI: 10.1021/jz201533w

Preparation of Uniform Needle-Like Aragonite Particles by Homogeneous Precipitation
journal, October 1999

  • Wang, Laifeng; Sondi, Ivan; Matijević, Egon
  • Journal of Colloid and Interface Science, Vol. 218, Issue 2
  • DOI: 10.1006/jcis.1999.6463

Derivation of an Accurate Force-Field for Simulating the Growth of Calcium Carbonate from Aqueous Solution: A New Model for the Calcite−Water Interface
journal, February 2010

  • Raiteri, Paolo; Gale, Julian D.; Quigley, David
  • The Journal of Physical Chemistry C, Vol. 114, Issue 13
  • DOI: 10.1021/jp910977a

Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption
journal, August 2012

  • Lopata, K.; Van Kuiken, B. E.; Khalil, M.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9
  • DOI: 10.1021/ct3005613

Local Aqueous Solvation Structure Around Ca 2+ During Ca 2+ ···Cl Pair Formation
journal, November 2015

  • Baer, Marcel D.; Mundy, Christopher J.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b09579

Aggregation-volume-bias Monte Carlo simulations of vapor-liquid nucleation barriers for Lennard-Jonesium
journal, December 2001

  • Chen, Bin; Siepmann, J. Ilja; Oh, Kwang J.
  • The Journal of Chemical Physics, Vol. 115, Issue 23
  • DOI: 10.1063/1.1417536

Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions
journal, August 2013


Quantitatively Probing the Al Distribution in Zeolites
journal, May 2014

  • Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja501361v

Prenucleation clusters and non-classical nucleation
journal, December 2011


A Microkinetic Model of Calcite Step Growth
journal, August 2016

  • Andersson, M. P.; Dobberschütz, S.; Sand, K. K.
  • Angewandte Chemie International Edition, Vol. 55, Issue 37
  • DOI: 10.1002/anie.201604357

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Revisiting the hydration structure of aqueous Na +
journal, February 2017

  • Galib, M.; Baer, M. D.; Skinner, L. B.
  • The Journal of Chemical Physics, Vol. 146, Issue 8
  • DOI: 10.1063/1.4975608

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Understanding the Effects of Concentration on the Solvation Structure of Ca 2+ in Aqueous Solution. I:  The Perspective on Local Structure from EXAFS and XANES
journal, June 2003

  • Fulton, John L.; Heald, Steve M.; Badyal, Yaspal S.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 23
  • DOI: 10.1021/jp0272264

Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 25, Issue 12
  • DOI: 10.1002/jcc.20078

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Thermodynamically Consistent Force Field for Molecular Dynamics Simulations of Alkaline-Earth Carbonates and Their Aqueous Speciation
journal, October 2015

  • Raiteri, Paolo; Demichelis, Raffaella; Gale, Julian D.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 43
  • DOI: 10.1021/acs.jpcc.5b07532

THE ORTHORHOMBIC STRUCTURE OF CaCO3, SrCO3, PbCO3 AND BaCO3: LINEAR STRUCTURAL TRENDS
journal, October 2009


Stable prenucleation mineral clusters are liquid-like ionic polymers
journal, September 2011

  • Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1604

Pseudopotentials for main group elements (IIIa through VIIa)
journal, December 1988


Role of CaCO 3 ° Neutral Pair in Calcium Carbonate Crystallization
journal, July 2016

  • Genovese, Damiano; Montalti, Marco; Otálora, Fermín
  • Crystal Growth & Design, Vol. 16, Issue 8
  • DOI: 10.1021/acs.cgd.6b00276

Investigation of volatile liquid surfaces by synchrotron x-ray spectroscopy of liquid microjets
journal, March 2004

  • Wilson, Kevin R.; Rude, Bruce S.; Smith, Jared
  • Review of Scientific Instruments, Vol. 75, Issue 3
  • DOI: 10.1063/1.1645656

Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
journal, December 2010

  • Raiteri, Paolo; Gale, Julian D.
  • Journal of the American Chemical Society, Vol. 132, Issue 49
  • DOI: 10.1021/ja108508k

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory
journal, November 2012

  • Zhang, Yu; Biggs, Jason D.; Healion, Daniel
  • The Journal of Chemical Physics, Vol. 137, Issue 19
  • DOI: 10.1063/1.4766356

Progress in the theory and interpretation of XANES
journal, January 2005


A hybrid Gaussian and plane wave density functional scheme
journal, October 1997

  • Lippert, By GERALD; Parrinello, JURG HUTTER and MICHELE
  • Molecular Physics, Vol. 92, Issue 3
  • DOI: 10.1080/002689797170220

Improving the Efficiency of the Aggregation−Volume−Bias Monte Carlo Algorithm
journal, November 2001

  • Chen, Bin; Siepmann, J. Ilja
  • The Journal of Physical Chemistry B, Vol. 105, Issue 45
  • DOI: 10.1021/jp012209k

Structural Characteristics of Synthetic Amorphous Calcium Carbonate
journal, July 2008

  • Michel, F. Marc; MacDonald, Jason; Feng, Jian
  • Chemistry of Materials, Vol. 20, Issue 14
  • DOI: 10.1021/cm800324v

The energetics of prenucleation clusters in lattice solutions
journal, December 2016

  • Legg, Benjamin A.; De Yoreo, James J.
  • The Journal of Chemical Physics, Vol. 145, Issue 21
  • DOI: 10.1063/1.4964489

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


A Straightforward Treatment of Activity in Aqueous CaCO 3 Solutions and the Consequences for Nucleation Theory
journal, December 2013

  • Kellermeier, Matthias; Picker, Andreas; Kempter, Andreas
  • Advanced Materials, Vol. 26, Issue 5
  • DOI: 10.1002/adma.201303643

Entropy Drives Calcium Carbonate Ion Association
journal, September 2016

  • Kellermeier, Matthias; Raiteri, Paolo; Berg, John K.
  • ChemPhysChem, Vol. 17, Issue 21
  • DOI: 10.1002/cphc.201600653

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
journal, December 2014

  • Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand
  • Inorganic Chemistry, Vol. 54, Issue 4
  • DOI: 10.1021/ic501991e

Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992

  • Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463940

Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)
journal, February 2012

  • Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu
  • Theoretical Chemistry Accounts, Vol. 131, Issue 2
  • DOI: 10.1007/s00214-012-1124-z

Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers
journal, May 2013

  • Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 21
  • DOI: 10.1021/jp401020j

A classical view on nonclassical nucleation
journal, September 2017

  • Smeets, Paul J. M.; Finney, Aaron R.; Habraken, Wouter J. E. M.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 38
  • DOI: 10.1073/pnas.1700342114

Forms and applications of the nucleation theorem
journal, July 2006

  • Kashchiev, Dimo
  • The Journal of Chemical Physics, Vol. 125, Issue 1
  • DOI: 10.1063/1.2210483

THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method
journal, October 1992

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130812

Stable Prenucleation Calcium Carbonate Clusters
journal, December 2008


Combined Sulfur K-Edge XANES–EXAFS Study of the Effect of Protonation on the Sulfate Tetrahedron in Solids and Solutions
journal, August 2013

  • Pin, S.; Huthwelker, T.; Brown, M. A.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 35
  • DOI: 10.1021/jp404272e

Monte Carlo Calculations of Effective Surface Tension for Small Clusters
journal, January 1996

  • N. Hale, Barbara
  • Australian Journal of Physics, Vol. 49, Issue 2
  • DOI: 10.1071/PH960425

LUCIA, a microfocus soft XAS beamline
journal, May 2006

  • Flank, A. -M.; Cauchon, G.; Lagarde, P.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 246, Issue 1
  • DOI: 10.1016/j.nimb.2005.12.007

The Aqueous Ca 2+ System, in Comparison with Zn 2+ , Fe 3 + , and Al 3 + : An Ab Initio Molecular Dynamics Study
journal, January 2013

  • Bogatko, Stuart; Cauët, Emilie; Bylaska, Eric
  • Chemistry - A European Journal, Vol. 19, Issue 9
  • DOI: 10.1002/chem.201202821

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory
journal, November 2015

  • Zhang, Yu; Mukamel, Shaul; Khalil, Munira
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 12
  • DOI: 10.1021/acs.jctc.5b00763

Comparative evaluation of the March and generalized spherical harmonic preferred orientation models using X-ray diffraction data for molybdite and calcite powders
journal, January 2005

  • Sitepu, Husin; O'Connor, Brian H.; Li, Deyu
  • Journal of Applied Crystallography, Vol. 38, Issue 1
  • DOI: 10.1107/S0021889804031231

The Initial Stages of Template-Controlled CaCO3 Formation Revealed by Cryo-TEM
journal, March 2009

  • Pouget, E. M.; Bomans, P. H. H.; Goos, J. A. C. M.
  • Science, Vol. 323, Issue 5920, p. 1455-1458
  • DOI: 10.1126/science.1169434

Ions interacting in solution: Moving from intrinsic to collective properties
journal, June 2016

  • Duignan, Timothy T.; Baer, Marcel D.; Mundy, Christopher J.
  • Current Opinion in Colloid & Interface Science, Vol. 23
  • DOI: 10.1016/j.cocis.2016.05.009

On the Phase Diagram of Calcium Carbonate Solutions
journal, June 2016

  • Zou, Zhaoyong; Habraken, Wouter J. E. M.; Bertinetti, Luca
  • Advanced Materials Interfaces, Vol. 4, Issue 1
  • DOI: 10.1002/admi.201600076

Thermodynamic-Kinetic Precipitation Modeling. A Case Study: The Amorphous Calcium Carbonate (ACC) Precipitation Pathway Unravelled
journal, March 2017

  • Carino, Agnese; Testino, Andrea; Andalibi, Mohammad Reza
  • Crystal Growth & Design, Vol. 17, Issue 4
  • DOI: 10.1021/acs.cgd.7b00006