Research

Geochemistry, mineralogy, and materials science specializing in application of chemical kinetics, mineral equilibria, molecular spectroscopy, and molecular simulation to complex multicomponent and multiphase systems; particular emphasis on the use of molecular simulation and various spectroscopies to understand material behavior.

Capabilities

Atomistic simulation with applications to geochemistry, materials science, and related areas.

  • Ion-ion and ion-surface potential of mean force calculations
  • Molecular dynamics (classical and ab initio)
  • Grand canonical Monte Carlo
  • Quantum chemistry (density functional theory)
  • Upscaling from atomistic to continuum-scale models
  • Aqueous speciation, solubility and reactive transport modeling
  • Adsorption and surface complexation modeling
  • Validation with spectroscopy (nuclear magnetic resonance, inelastic neutron scattering, infrared/Raman)

Molecular Geochemistry Facilities

Red Sky is a 217-teraflop supercomputer at Sandia National Laboratories, comprised of SUN X6275 blades with 18,544 computing cores.

Red Sky is a 217-teraflop supercomputer at Sandia National Laboratories, comprised of SUN X6275 blades with 18,544 computing cores.

Geochemistry group computer clusters; 28 node AMD and Intel clusters with 192 processors.

Geochemistry group computer clusters; 28 node AMD and Intel clusters with 192 processors.

Publications

  • R.T. Cygan, J.E. Post, P.J. Heaney, and J.D. Kubicki (2012) Molecular models of birnessite and related hydrated layered minerals. American Mineralogist, 97(8-9), 1505-1514. http://dx.doi.org/10.2138/am.2012.3957
  • R.T. Cygan, V.N. Romanov, and E.M. Myshakin (2012) Molecular simulation of carbon dioxide capture by montmorillonite using an accurate and flexible force field. Journal of Physical Chemistry C, 116(24), 13079-13091. http://dx.doi.org/10.1021/jp3007574
  • J.A. Greathouse and R.T. Cygan. (2012) Molecular Simulations of Clay Minerals. in Handbook of Clay Science, F. Bergaya and B.K.G. Theng, Eds., Elsevier, in press.
  • J.A. Greathouse, D.B. Hart, M.E. Ochs (2012) Alcohol and Thiol Adsorption on (Oxy)hydroxide and Carbon Surfaces: Molecular Dynamics Simulation and Desorption Experiments. Journal of Physical Chemistry C, 116, 26756-26764. http://dx.doi.org/10.1021/jp305275q
  • S.L. Teich-McGoldrick, J.A. Greathouse, R.T. Cygan. (2012) Molecular Dynamics Simulations of Structural and Mechanical Properties of Muscovite: Pressure and Temperature Effects. Journal of Physical Chemistry C, 116, 15099-15107. http://dx.doi.org/ 10.1021/jp303143s
  • T.R. Zeitler, J.A. Greathouse, and R.T. Cygan, (2012) Effects of Thermodynamic Ensembles and Mineral Surfaces on Interfacial Water Structure. Physical Chemistry Chemical Physics, 14(5), 1728-1734. http://dx.doi.org/10.1039/C2CP22593J
  • G. Zhang, Z. Wei, R.E. Ferrell, S.J. Guggenheim, R.T. Cygan, and J. Luo (2010) Evaluation of the elasticity normal to the basal plane of non-expandable 2:1 phyllosilicates by nanoindentation. American Mineralogist, 95(5-6), 863-869. http://dx.doi.org/10.2138/am.2010.3398
  • R.T. Cygan, J.A. Greathouse, H. Heinz, A.G. Kalinichev (2009) Molecular models and simulations of layered materials. Journal of Materials Chemistry, 19(17), 2470-2481. http://dx.doi.org/10.1039/b819076c
  • J.A. Greathouse, J.S. Durkin, J.P. Larentzos, R.T. Cygan (2009) Implementation of a Morse potential to model hydroxyl behavior in phyllosilicates. Journal of Chemical Physics, 130(13), 134713. http://dx.doi.org/10.1063/1.3103886
  • N.W. Ockwig, J.A. Greathouse, J.S. Durkin, R.T. Cygan, L.L. Daemen, and T.M. Nenoff (2009) Nanoconfined water in magnesium-rich 2:1 phyllosilicates. Journal of the American Chemical Society, 131(23), 8155-8162. http://dx.doi.org/10.1021/ja900812m
  • J.P. Larentzos, J.A. Greathouse, and R.T. Cygan (2007) An ab initio and classical molecular dynamics investigation of the structural and vibrational properties of talc and pyrophyllite. Journal of Physical Chemistry C, 111(34), 12752-12759. http://dx.doi.org/10.1021/jp072959f
  • I.F. Vasconcelos, B.A. Bunker, and R.T. Cygan (2007) Molecular dynamics modeling of ion adsorption to the basal surfaces of kaolinite. Journal of Physical Chemistry C, 111(18), 6753-6762. http://dx.doi.org/10.1021/jp065687
  • P.S. Braterman and R.T. Cygan (2006) Vibrational spectroscopy of brucite: A molecular simulation investigation. American Mineralogist, 91(7), 1188-1196. http://dx.doi.org/10.2138/am.2006.2094
  • J.A. Greathouse and R.T. Cygan (2006) Water structure and aqueous uranyl (VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: Results from molecular simulations. Environmental Science & Technology, 40(12), 3865-3871. http://dx.doi.org/10.1021/es052522q
  • J.A. Greathouse and R.T. Cygan (2005) Molecular dynamics simulation of uranyl(VI) sorption equilibria onto an external montmorillonite surface. Physical Chemistry Chemical Physics, 7(20), 3580-3586. http://dx.doi.org/10.1039/b509307d
  • J. Wang, A.G. Kalinichev, R.J. Kirkpatrick, and R.T. Cygan (2005) Structure, energetics, and dynamics of water adsorbed on the muscovite (001) surface: A molecular dynamics simulation. Journal of Physical Chemistry B, 109(33), 15893-15905. http://dx.doi.org/10.1021/jp045299c
  • L.J. Criscenti and R.T. Cygan (2012) Molecular simulations of carbon dioxide and water: Cation solvation. Environmental Science & Technology, 116, in press. http://dx.doi.org/10.1021/es301608c
  • Katz, L.E., Criscenti, L.J., Chen, C.C., Larentzos, J.P., and Liljestrand, H.M. (2012) Temperature effects on alkaline earth metal ions adsorption on gibbsite: Approaches from macroscopic sorption experiments and molecular dynamics simulations. Journal of Colloid and Interface Science, http://dx.doi.org/10.1016/j.jcis.2012.05.011
  • Leung, K. and Criscenti, L.J. (2012) Predicting the pKa of a goethite hydroxyl group from first principles. Journal of Physics: Condensed Matter, invited, http://dx.doi.org/10.1088/0953-8984/24/12/124105
  • Leung, K., Nielsen, I. M. B., and Criscenti, L. J. (2009) Elucidating the bimodal acid-base behavior of the water-silica interface from first principles. Journal of American Chemical Society, 131, 18358-18365. http://dx.doi.org/10.1021/ja906190t
  • Carroll, S., S. Roberts, L.J. Criscenti, and P.A. O’Day (2008) Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite. Geochemical Transactions, 9, article 2. http://dx.doi.org/10.1186/1467-4866-9-2
  • Goldberg, S. and L.J. Criscenti (2008) Modeling adsorption of heavy metals and metalloids by soil components.In: Biophysico-chemical processes of heavy metals and metalloids in soil environments. A. Violante, P. M. Huang, and G. Gadd (eds.), John Wiley and Sons, Chichester, England.
  • Larentzos, J. P. and Criscenti, L. J. (2008) A molecular dynamics study of alkaline earth metal-chloride complexation in aqueous solution. Journal of Physical Chemistry B, 112(45), 14243-14250.
  • Xu, M., J. P. Larentzos, M. Roshdy, L.J. Criscenti, and H. C. Allen (2008) Aqueous divalent metal-nitrate interactions: hydration versus ion pairing. Physical Chemistry Chemical Physics, 10, 4793-4801.
  • Goldberg, S., L.J. Criscenti, D.R. Turner, J. A. Davis, and K. J. Cantrell (2007) Adsorption-desorption processes in subsurface reactive transport modeling. Vadose Zone Journal, 6, 407-435.
  • Criscenti, L.J., J.D. Kubicki, and S.L. Brantley (2006) Silicate glass and mineral dissolution: calculated reaction paths and activation energies for hydrolysis of a Q3 Si by H3O+ using ab initio methods. Journal of Physical Chemistry A, 110, 198-206. http://dx.doi.org/10.1021/jp044360a
  • Criscenti, L. J., S. L. Brantley, K. T. Mueller, N. Tsomaia, and J. D. Kubicki (2005) Theoretical and 27Al CPMAS NMR Investigation of Aluminum Coordination Changes During Aluminosilicate Dissolution. Geochimica et Cosmochimica Acta, 69, 2205-2220. http://dx.doi.org/10.1016/j.gca.2004.10.020
  • L.J. Criscenti, R.T. Cygan, A.S. Kooser, and H.K. Moffat (2008) Water and halide adsorption to corrosion surfaces: Molecular simulations of atmospheric interactions with aluminum oxyhydroxide and gold. Chemistry of Materials, 20(14), 4682-4693. http://dx.doi.org/10.1021%2Fcm702781r
  • R.T. Cygan, C.T. Stevens, R.W. Puls, S.B. Yabusaki, R.D. Wauchope, C.J. McGrath, C.J., G.P. Curtis, M.D. Siegel, L.A. Veblen, and D.R. Turner (2007) Research activities at U.S. government agencies in subsurface reactive transport modeling. Vadose Zone Journal, 6(4), 805-822. http://dx.doi.org/10.2136/vzj2006.0091
  • T.D. Perry, R.T. Cygan, and R. Mitchell (2007) Molecular models of a hydrated calcite mineral surface. Geochimica et Cosmochimica Acta, 71(24), 5876-5887. http://dx.doi.org/10.1016/j.gca.2007.08.030
  • K.J. Johnson, R.T. Cygan, and J.B. Fein (2006) Molecular simulations of metal adsorption to bacterial surfaces. Geochimica et Cosmochimica Acta, 70(20), 5075-5088. http://dx.doi.org/10.1016/j.gca.2006.07.028
  • T.D. Perry, R.T. Cygan, and R. Mitchell (2006) Molecular models of alginic acid: Interactions with calcium ions and calcite surfaces. Geochimica et Cosmochimica Acta, 70(14), 3508-3532. http://dx.doi.org/10.1016/j.gca.2007.08.030
  • S.J. Altman, M.L. Rivers, M. Reno, R.T. Cygan, and A.A. McLain (2005) Characterization of sorption sites on aggregate soil samples using synchrotron X-ray computerized microtomography. Environmental Science & Technology, 39(8), 2679-2685. http://dx.doi.org/10.1021/es049103y
  • J.S. Clawson, R.T. Cygan, T.M. Alam, K. Leung, and S.B. Rempe (2010) Ab initio study of hydrogen storage in water clathrates. Journal of Computational and Theoretical Nanoscience, 7(12), 2602-2606. http://dx.doi.org/10.1166/jctn.2010.1648
  • J.A. Greathouse, R.T. Cygan, R.A. Bradshaw, E.H. Majzoub, and B.A. Simmons (2007) Computational and spectroscopic studies of dichlorofluroethane hydrate structure and stability. Journal of Physical Chemistry C, 111(45), 16787-16795. http://dx.doi.org/10.1021/jp072968o
  • J.A. Greathouse, R.T. Cygan, and B.A. Simmons (2006) Vibrational spectra of methane clathrate hydrates from molecular dynamics simulation. Journal of Physical Chemistry B, 110(13), 6428-6431. http://dx.doi.org/10.1021/jp060471t
  • Hou, Y., Fang, X., Kwon, K., Criscenti, L.J., Davis, D., Lambert, T. and Nyman, M. (accepted) Computational and Experimental Characterization and Corroboration of a Cagelike Fe15 Polycation. European Journal of Inorganic Chemistry, Special Issue for Mike Pope’s 80th birthday.
  • Zeitler, T. and Criscenti, L.J. (accepted) Classical Potentials for Nuclear Materials. Chapter for OECD/NEA Volume on Multi-scale Materials Modeling. Invited by V. Tikare, Chair of OECD NEA Expert Group on Multi-scale Materials Modeling.
  • S.T. Meek, S.L. Teich-McGoldrick, J.J. Perry, J.A. Greathouse, and M.D. Allendorf. (2012) Effects of Polarizability on the Adsorption of Noble Gases at Low Pressures in Monohalogenated Isoreticular Metal-Organic Frameworks. Journal of Physical Chemistry C, 116, 19765-19772. http://dx.doi.org/10.1021/jp303274m
  • A.L. Robinson, V. Stavila, T.R. Zeitler, M.I. White, S.M. Thornberg, J.A. Greathouse, M.D. Allendorf. (2012) Ultrasensitive Humidity Detection Using Metal–Organic Framework-Coated Microsensors. Analytical Chemistry, 84, 7043-7051. http://dx.doi.org/10.1021/ac301183w
  • T. Van Heest, S.L. Teich-McGoldrick, J.A. Greathouse, M.D. Allendorf, D.S. Sholl. (2012) Identification of metal-organic framework materials for adsorption separation of rare gases: Applicability of IAST and effects of inaccessible framework regions. Journal of Physical Chemistry C, 116, 13183-13195. http://dx.doi.org/ 10.1021/jp302808j
  • T.R. Zeitler, M.D. Allendorf, J.A. Greathouse (2012) Grand Canonical Monte Carlo Simulation of Low-pressure Methane Adsorption in Nanoporous Framework Materials for Sensing Applications. Journal of Physical Chemistry C, in press. http://dx.doi.org/10.1021/jp208596e
  • D.F. Sava, M.A. Rodriguez, K.W. Chapman, P.J. Chupas, J.A. Greathouse, P.S. Crozier, and T.M. Nenoff, (2011) Capture of Volatile Iodine, a Gaseous Fission Product, by Zeolitic Imidazolate Framework-8. Journal of the American Chemical Society, 133(32), 12398-12401. http://dx.doi.org/10.1021/ja204757x
  • S.T. Meek, J.J. Perry, S. Teich-McGoldrick, J.A. Greathouse, and M.D. Allendorf (2011) Complete Series of Mono-Halogenated Isoreticular Metal-Organic Frameworks: Synthesis and the Importance of Activation Method. Crystal Growth & Design, 23, 249-267. http://dx.doi.org/10.1021/cg201136k
  • S.T. Meek, J.A. Greathouse, and M.D. Allendorf (2011) Metal-Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials. Advanced Materials, 23, 249-267. http://dx.doi.org/10.1002/adma.201002854
  • J.A. Greathouse, N.W. Ockwig, L.J. Criscenti, T.R. Guilinger, P. Pohl, and M.D. Allendorf (2010) Computational screening of metal-organic frameworks for large-molecule chemical Sensing. Physical Chemistry Chemical Physics,12(39), 12621-12629. http://dx.doi.org/10.1039/C0CP00092B
  • R.K. Raghunandan, J.L. Herberg, B. Jacobs, A. Highley, R. Behrens, N.W. Ockwig, J.A. Greathouse, and M.D. Allendorf (2009) Metal-organic frameworks as templates for nanoscale NaAlH4. Journal of the American Chemical Society, 131(37), 13198-13199. http://dx.doi.org/10.1021/ja904431x
  • J.A. Greathouse and M.D. Allendorf (2009) Adsorption and separation of noble gases by IRMOF-1: Grand canonical Monte Carlo simulations. Industrial & Engineering Chemistry Research. 48(7), 3425-3431. http://dx.doi.org/10.1021/ie801294n
  • J.A. Greathouse and M.D. Allendorf (2008) Force field validation for molecular dynamics simulations of IRMOF-1 and other isoreticular zinc carboxylate coordination polymers. Journal of Physical Chemistry C, 112, 5795-5802. http://dx.doi.org/10.1021/jp076853w
  • N.W. Ockwig, R.T. Cygan, L.J. Criscenti, and T.M. Nenoff (2008) Molecular dynamics studies of nanoconfined water in clinoptilolite and heulandite zeolites. Physical Chemistry Chemical Physics, 10(6), 800-807. http://dx.doi.org/10.1039/b711949f
  • N.W. Ockwig, R.T. Cygan, M.A. Hartl, L.L. Daemen, and T.M. Nenoff (2008) Incoherent inelastic neutron scattering studies of nanoconfined water in clinoptilolite and heulandite zeolites. Journal of Physical Chemistry C, 112(35), 13629-13634. http://dx.doi.org/10.1021%2Fjp803770v
  • T.M. Nenoff, N.W. Ockwig, R.T. Cygan, T.M. Alam, K. Leung, J.D. Pless, H. Xu, M.A. Hartl, and L.L. Daemen (2007) Role of water in selectivity of niobate-based octahedral molecular sieves. Journal of Physical Chemistry C, 111(35), 13212-13221. http://dx.doi.org/10.1021/jp073969j
  • J.A. Greathouse and M.D. Allendorf (2006) The interaction of water with MOF-5 simulated by molecular dynamics. Journal of the American Chemical Society, 128, 10678-10679. http://dx.doi.org/10.1021/ja063506b
  • Zeitler, T. and Criscenti, L.J. (accepted) Classical Potentials for Nuclear Materials. Chapter for OECD/NEA Volume on Multi-scale Materials Modeling. Invited by V. Tikare, Chair of OECD NEA Expert Group on Multi-scale Materials Modeling.
  • A.E. Ismail, J.A. Greathouse, P.S. Crozier, and S.M. Foiles (2010) Electron-ion coupling effects on simulations of radiation damage in pyrochlore waste forms. Journal of Physics: Condensed Matter, 22(22), 225405. http://dx.doi.org/10.1088/0953-8984/22/22/225405
  • R.T. Cygan, C.J. Brinker, M.D. Nyman, K. Leung, and S.L. Rempe (2008) A molecular basis for advanced materials in water treatment. Materials Research Society Bulletin, 33(1), 42-47. http://www.mrs.org/s_mrs/sec_subscribe.asp?CID=13460&DID=207079&action=detail
  • L.J. Criscenti, P.A. Schultz, C. Steefel, P. Zapol, I. Bourg (2011) Progress toward Bridging from Atomistic to Continuum Modeling to Predict Nuclear Waste Glass Dissolution. Report SAND2011-8250, Sandia National Laboratories.
  • JV Ryan, WL Ebert, JP Icenhower, DM Strachan, CI Steefel, LJ Criscenti, IC Bourg, RE Williford, KA Murphy, EM Pierce, CM Jantzen, DK Shuh, GA Waychunas, JC Marra, JP Vienna, P Zapol (2011) Technical Program Plan for the International Technical Evaluation of Alteration Mechanisms (I-TEAM) , PNNL-21031.
  • Arguello, J.G. Jr., Criscenti. L.J., Dewers, T.A., Sassani, D.C., Wang, Y., Schultz, P.A., Edwards, H.C., Bouchard, J.F., Freeze, G.A. 2011. Nuclear Energy Advanced Modeling and Simulation (NEAMS) Waste Integrated Performance and Safety Codes (IPSC): FY10 development and integration. SAND 2011-0845.
  • Criscenti, L.J. and Sassani, D. 2010. Upscaling Atomistic Mechanisms to Continuum Models for Nuclear Waste Glass Dissolution, FMM NEAMS Project Report/SAND Report 2010-6707P.
  • Criscenti, L.J. and Bracco, J. 2010. Molecular modeling in support of CO2 sequestration and enhanced oil recovery.  SAND2011-0257. Sandia National Laboratories, Albuquerque, NM.
  • Criscenti, L.J. and Ockwig, N.W. 2009. Investigation of biologically-designed metal-specific chelators for potential metal recovery and waste remediation applications.  SAND2009-0239. Sandia National Laboratories, Albuquerque, NM.
  • Leung, K., Nenoff, T.M., Criscenti, L.J., Tang, Z. and Dong, J.H. 2008. Capturing CO2 via reactions in nanopores. SAND2008-7053, Sandia National Laboratories, Albuquerque, NM.
  • Criscenti, L.J., M. Eliassi, R.T. Cygan, C. F. Jové Cólón, and S. Goldberg 2006. Modeling Adsorption Processes:  Issues in Uncertainty, Scaling, and Prediction. U.S. Nuclear Regulatory Commission.  NUREG/CP-6893.
  • Cygan, R.T., Siegel, M.D., and Criscenti, L.J. 2006. Proceedings of the International Workshop on Conceptual Model Development for Subsurface Reactive Transport Modeling of Inorganic Contaminants, Radionuclides, and Nutrients.  U.S. Nuclear Regulatory Commission. NUREG/CP-0193.
  • F.D. Hansen, E.L. Hardin, R.P. Rechard, G.A. Freeze, D.C. Sassani, P.V. Brady, C.M. Stone, M.J. Martinez, J.F. Holland, T. Dewers, K.N. Gaither, S.R. Sobolik, and R.T. Cygan (2010) Shale disposal of U.S. high-level radioactive waste.  Report SAND2010-2843, Sandia National Laboratories.
  • R.W. Bradshaw, J.A. Greathouse, R.T. Cygan, B.A. Simmons, D.E. Dedrick, and E.H. Majzoub (2008) Desalination utilizing clathrate hydrates (LDRD final report).  Report SAND2007-6565, Sandia National Laboratories.
  • R.T. Cygan, T.M. Alam, C.J. Brinker, B.C. Bunker, J.S. Clawson, L.J. Criscenti, P.S. Crozier, D. Farrow, P.J. Feibelman, B.L. Frankamp, G.P. Holland, J.E. Houston, D.L. Huber, Y.-B. Jiang, K. Leung, C.D. Lorenz, T.M. Nenoff, M.D. Nyman, N.W. Ockwig, C.J. Orendorff, J.D. Pless, S.B. Rempe, S. Singh, M.J. Stevens, K. Thuermer, F.B. van Swol, S. Varma, R.C. Major, M.J. McGrath, J.I. Sepmann, X. Zhu, J.L. Cecchi, Z. Chen, D.R. Dunphy, H. Gerung, D.J. Kissel, N. Liu, G.K. Xomeritakis, J.A. Anderson, A. Travesset, L.L. Daemen, M.A. Hartl, and H. Xu (2008) Exploiting interfacial water properties for desalination and purification applications.  Report SAND2008-5729, Sandia National Laboratories.
  • J.A. Greathouse, M.D. Allendorf, and J.C. Sanders (2008) Computational investigation of noble gas adsorption and separation by nanoporous materials.  Report SAND2008-6687, Sandia National Laboratories.
  • G.E. Hammond and R.T. Cygan (2007) Geoquìmico:  An interactive tool for comparing sorption conceptual models (surface complexation modeling versus KD).  Report SAND2007-7091, Sandia National Laboratories.
  • S.L. Rempe, D. Sabo, J.S. Clawson, J.A. Greathouse, K. Leung, R.T. Cygan, M.G. Martin, T.M. Alam, and S. Varma (2007) Fuel traps:  Mapping stability via water association.  Report SAND2007-1643, Sandia National Laboratories.
  • R.T. Cygan and J.A. Greathouse (2005) Frontiers of interfacial water research:  Workshop report.  Report SAND2005-6220, Sandia National Laboratories.
  • Z.R. Tian, L.J. Criscenti, E.D. Spoerke, B.B. McKenzie, R.T. Cygan, J.A. Voigt, and M.L. Machesky (2005) Solution-based nanoengineering of materials.  Report SAND2005-0860, Sandia National Laboratories.