(gc3564)Nanostructure Formation, Aggregation, and Reactivity
EMSL Project ID
3564
Abstract
This project is the outgrowth of several projects currently funded by DOE-BES at PNNL and ANL or new proposals co-authored by the participants and submitted to DOE?s Computational Nanoscience initiative involving two complementary efforts that focus on the fundamental characterization of nanomaterials: their synthesis and their reactivity. These proposed studies draw on advanced and novel methodologies that are being developed in these projects and that are intended and designed to take full advantage of state-of-the-art computing capabilities such as those available at PNNL?s EMSL to broadly advance the field of modeling in nanoscience.The goal of the computational research on nanomaterial synthesis is to provide a comprehensive understanding of nucleation, growth, and aggregation relevant to nanotechnology through the application of simulation methods and tools, aiming at getting a handle on control of size, composition, structure, and properties of nanoscale building block components. Capabilities are being developed to understand, predict, and control production rate and characteristics of these fundamental building blocks and their dependence on external factors. Specific research subjects to be investigated in this are are: i) Molecular dynamics simulations of fullerene growth mechanisms by investigating the aggregation behavior of C2 molecular units under high temperature and pressure and subsequent cluster growth toward cage closure. ii) Molecular dynamics simulations for the interconversion of carbon onions into carbon spiroids. iii) The systematic simulation in parameter space (temperature and ionic concentration) of crystalline phase growth in solution, for example CdSe in organic solvent, for the fabrication of nano-electronic devices.
The goal of the computational research on nanomaterial reactivity is to obtain a characterization of reactivity in the nanoscale using several advanced and novel methods being developed. These new computational tools are specifically targeted at the quantum chemical characterization of structures, properties, and reactivity in the nanoscale. With the unique computing capabilities offered by the EMSL facility, these tools will provide the ability to carry out quantum chemical electronic structure calculations on systems heretofore not accessible, with up to 105 atoms, i.e. in the nano range, using a reliable and well calibrated reduced-requirement density functional-based tight binding method (DFTB). Embedding of this model into an physical and chemical environment to capture electronic and structural effects at different scales will be achieved through the coupling to the ONIOM protocol that permits combination of methods of variable fidelity, as well as a seamless approach, termed the Generalized Quasi-Continuum method (GQC), that couples fully resolved atomic scale regions with coarse-grained regions via a finite-element-like methodology, which will allow to investigate systems of up to several 1000 nm in size. The potential of the newly developed methods will be tested and benchmarked in selected studies dealing with the formation of nanosystems, their structure, and their reactivity. Specific research subjects to be investigated in this are are: i) Characterization of the formation mechanisms of carbon nanotubes and fullerenes from pure carbon and SiC compounds in the presence or absence of metal catalysts, and of their reactivity toward their oxidation and functionalization. ii) Characterization of the structure and thermal and non-thermal reactivity of metal/metal oxide nanoparticles (Cr2O3/Fe2O3, SrTiO3/Si) and of their catalytic activity (reaction specificity) as a function of their structure, composition, and size. iii) Characterization of thermal stability and growth of High-K material interfaces with silicon. iv) Investigation of the structures of nanoporous metal oxide (aluminum oxide, vanadium oxide) membranes and reactions pathways for catalytic reactions such as hydrocarbon dehydrogenation occurring on the surfaces of the pores.
Project Details
Project type
Capability Research
Start Date
2003-10-01
End Date
2006-10-08
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Barnard AS, and LA Curtiss. 2006. "Predicting the Shape and Structure of Face- Centered Cubic Gold Nanocrystals Smaller than 3 nm." Chemphyschem 7(7):1544-1553. doi:10.1002/cphc.200600107
Barnard AS, and LA Curtiss. 2007. "Modeling the Preferred Shape, Orientation and Aspect Ratio of Gold Nanorods." Journal of Materials Chemistry 17:3315-3323.
Barnard AS, and MG Sternberg. 2005. "Substitutional Nitrogen in Nanodiamond and Bucky-Diamond Particles." Journal of Physical Chemistry B 109(36):17107-17112. doi:10.1021/jp0524126
Barnard AS, and MG Sternberg. 2006. "Substitutional Boron in Nanodiamond, Bucky-Diamond, and Nanocrystalline Diamond Grain Boundaries." Journal of Physical Chemistry B 110(39):19307-19314. doi:10.1021/jp0634252
Barnard AS, and P Zapol. 2004. "A Model for the Phase Stability of Arbitrary Nanoparticles as a Function of Size and Shape." Journal of Chemical Physics 121(9):4276-4283 . doi:10.1063/1.1775770
Barnard AS, and P Zapol. 2004. "Effects of Particle Morphology and Surface Hydrogenation on the Phase Stability of TiO2 at the Nanoscale." Physical Review. B, Condensed Matter and Materials Physics 70(23):Art. No. 235403. doi:10.1103/PhysRevB.70.235403
Barnard AS, and P Zapol. 2004. "Predicting the Energetics, Phase Stability and Morphology Evolution of Faceted and Spherical Anatase Nanocrystals." Journal of Physical Chemistry B 108 (48):18435 -18440. doi:10.1021/jp0472459 S1089-5647(04)07245-1
Barnard AS, P Zapol, and LA Curtiss. 2005. "Modeling the Morphology and Phase Stability of TiO2 Nanocrystals in Water." Journal of Chemical Theory and Computation 1(1):107-116.
Barnard AS, P Zapol, and L Curtiss. 2005. "Anatase and Rutile Surfaces with Adsorbates Representative of Acidic and Basic Conditions." Surface Science 582:173-188. doi:10.1016/j.susc.2005.03.014
Barnard AS, S Erdin, Y Lin, P Zapol, and JW Halley. 2006. "Modeling the Structure and Electronic Properties of TiO? Nanoparticles." Physical Review. B, Condensed Matter 73:205405 1-8. doi:10.1103/PhysRevB.73.205405
Barnard AS, XM Lin, and L Curtiss. 2005. "Equilibrium Morphology of Face-Centered Cubic Gold Nanoparticles >3 nm and the Shape Changes Induced by Temperature." Journal of Physical Chemistry B 109(51):24465-24472. doi:10.1021/jp054279n
Bylaska EJ, KL Tsemekhman, SB Baden, JH Weare, and H Jonsson. 2011. "Parallel Implementation of Gamma-Point Pseudopotential Plane-Wave DFT with Exact Exchange." Journal of Computational Chemistry 32(1):54-69.
Deskins NA, and M Dupuis. 2007. "Electron Transport via Polaron Hopping in Bulk TiO2: a density functional theory characterization." Physical Review. B, Condensed Matter and Materials Physics 75(19):Art. No. 195212. doi:10.1103/PhysRevB.75.195212
Deskins NA, and M Dupuis. 2007. "Electron Transport via Polaron Hopping in Bulk TiO(sub 2): a density functional theory characterization." Physical Review. B, Condensed Matter and Materials Physics 75(19):Art. No. 195212
Deskins NA, and M Dupuis. 2009. " Intrinsic Hole Migration Rates in TiO2 from Density Functional Theory." Journal of Physical Chemistry C 113(1):346-358.
Deskins, N. A. Chemical Physics Letters 2009, 471, 75.
Deskins NA, RJ Rousseau, and M Dupuis. 2009. "Localized Electronic States from Surface Hydroxyls and Polarons in TiO2(110)." Journal of Physical Chemistry C 113(33):14583-14586 .
Deskins NA, SN Kerisit, KM Rosso, and M Dupuis. 2007. "Molecular Dynamics Characterization of Rutile-Anatase Interfaces." Journal of Physical Chemistry C 111(26):9290-9298.
Deskins NA, SN Kerisit, KM Rosso, and M Dupuis. 2007. "Molecular Dynamics Characterization of Rutile-Anatase Interfaces." Journal of Physical Chemistry C 111(26):9290-9298. doi:10.1021/jp0713211
Du, Y.; Deskins, N. A.; Zhang, Z.; Dohnalek, Z.; Dupuis, M.; Lyubinetsky, I. Physical Review Letters 2009, 102, 096102.
Du, Y. G.; Deskins, N. A.; Zhang, Z. R.; Dohnalek, Z.; Dupuis, M.; Lyubinetsky, I. Journal of Physical Chemistry C 2009, 113, 666.
Feng X, S Irle, HA Witek, K Morokuma, R Vidic, and E Borguet. 2005. "Sensitivity of Ammonia Interaction with Single-Walled Carbon Nanotube Bundles to the Presence of Defect Sites and Functionalities." Journal of the American Chemical Society 127(30):10533-10538.
Iddir H, DD Fong, P Zapol, PH Fuoss, LA Curtiss, GW Zhou, and JA Eastman. 2007. "Order-disorder Phase Transition of the Cu(001) Surface under Equilibrium Oxygen Pressure." Physical Review. B, Condensed Matter 76:241404(R). doi:10.1103/PhysRevB.76.241404
Iddir H, V Komanicky, S Ogut, H You, and P Zapol. 2007. "Shape of Platinum Nanoparticles Supported on SrTiO₃: Experiment and Theory." Journal of Physical Chemistry C 111(40):14782-14789.
Iordanova NI, M Dupuis, and KM Rosso. 2005. "Charge Transport in Metal Oxides: A Theoretical Study of Hematite α-Fe2O3 ." Journal of Chemical Physics 122(14):144305.
Iordanova NI, M Dupuis, and KM Rosso. 2005. "Theoretical Characterization of Charge Transport in Chromia (α-Cr2O3)." Journal of Chemical Physics 123(7):074710 (1-11).
Irle S, G Zheng, Z Wang, and K Morokuma. 2006. "The C60 Formation Puzzle "Solved": QM/MD Simulations Reveal the Shrinking Hot Giant Road of the Dynamic Fullerene Self-Assembly Mechanism." Journal of Physical Chemistry B 110:14531-14545.
Irle S, Z Wang, G Zheng, K Morokuma, and M Kusunoki. 2006. "Theory and experiment agree: Single-walled carbon nanotube caps
grow catalyst-free with chirality preference on a SiC surface." Journal of Chemical Physics 125:044702.
Kerisit SN, NA Deskins, KM Rosso, and M Dupuis. 2008. "A Shell Model for Atomistic Simulation of Charge Transfer in Titania." Journal of Physical Chemistry C 112(20):7678-7688. doi:10.1021/jp8007865
Lei Y, F Mehmood, SS Lee, JP Greeley, B Lee, S Seifert, RE Winans, JW Elam, RJ Meyer, PC Redfern, D Teschner, R Schlogl, MJ Pellin, LA Curtiss, and S Vajda. 2010. "Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects." Science 328(5975):224-228. doi:10.1126/science.1185200
Rosso KM, and M Dupuis. 2004. "Reorganization Energy Associated with Small Polaron Mobility in Iron Oxide." Journal of Chemical Physics 120(15):7050-7054.
Rosso KM, D Smith, and M Dupuis. 2003. "An Ab Initio Model of Electron Transport in Hematite (a-Fe2O3) Basal Planes." Journal of Chemical Physics 118(14):6455-6466.
Strmcnik DS, DV Tripkovic, D van der Vliet, KC Chang, V Komanicky, H You, G Karapetrov, JP Greeley, VR Stamenkovic, and NM Markovic. 2008. "Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction." Journal of the American Chemical Society 130(46):15332-15339. doi:10.1021/ja8032185
Wang Z, S Irle, G Zheng, and K Morokuma. 2008. "Analysis of the Relationship between Reaction Energies of Electrophilic SWNT Additions and Sidewall Curvature: Chiral Nanotubes." Journal of Physical Chemistry C 112(33):12697-12705. doi:10.1021/jp802964c
Wang Z, S Irle, G Zheng, K Morokuma, M Kusunoki. 2007. "Carbon Nanotubes Grow on the C Face of SiC (000(1) over-bar) during Sublimation Decomposition: Quantum Chemical Molecular Dynamics Simulations." J. Phys. Chem. C, 111, 12960-12972
Witek HA, S Irle, G Zheng, WA De Jong, and K Morokuma. 2006. "Modeling Carbon Nanostructures with the Self-Consistent Charge Density-Functional Tight-Binding Method: Vibrational Spectra and Electronic Structure of C(sub 28), C(sub 60), and C(sub 70)." Journal of Chemical Physics 125(21):Art. No. 214706.
Zheng G, S Irle, and K Morokuma. 2004. "Towards Formation of Buckminsterfullerene C60 in Quantum Chemical Molecular Dynamics." Journal of Chemical Physics 122:Art No. 014708.
Zheng G, S Irle, and K Morokuma. 2005. "Performance of the DFTB method in comparison to DFT and semiempirical methods for geometries and energies of C20–C86 fullerene isomers." Chemical Physics Letters 412(1-3):210-216. doi:10.1016/j.cplett.2005.06.105
Zheng G, S Irle, M Elstner, and K Morokuma. 2004. "Quantum Chemical Molecular Dynamics Model Study of Fullerene Formation from Open-Ended Carbon Nanotubes." Journal of Physical Chemistry A 108(15):3182-3194.
Zheng G, Z Wang, S Irle, and K Morokuma. 2006. "Origin of the Linear Relationship between CH2/NH/O-SWNT Reaction Energies and Sidewall Curvature: Armchair Nanotubes." Journal of the American Chemical Society 128(47):15117-15126.