Computational Studies of Nanoparticle Formation and Bulk Properties for Biomineralization
EMSL Project ID
50727
Abstract
There is a critical need to develop an understanding of nanoparticle and mineral formation in systems that contain H2O, metal ions and CO2 as carbonation and hydrolysis reactions are important for the formation of minerals and their dissolution. Such processes are highly relevant to carbon dioxide capture and sequestration as well as well as to biomineralization and carbon cycling. We propose computational electronic structure studies of a variety of processes relevant to the formation of nanoparticles and minerals of the metal dications Mg2+, Ca2+, and Fe2+ in the presence of H2O and CO2. We propose to use advanced computational chemistry approaches implemented on EMSL's massively parallel computers to develop a quantitative description of these particle formation processes to develop new understanding of the physical phenomena that occur at different spatial and temporal scales that underlie such behavior. We will use computational chemistry approaches at the density functional theory (molecular and plane-wave) and correlated molecular orbital theory levels to study a range of processes. (1) We will continue to predict the formation of nanoparticles from the ground up starting with monomers. (2) We will continue to predict reliable heats of formation of monomers to predict cohesive energies of bulk minerals. (3) We will continue to predict reliable heats of formation of ultrasmall nanoparticles to serve as benchmarks for methods to predict the energetics of larger molecules. (4) We will continue to use ab initio density functional theory approaches to predict energetic properties of minerals and predict how carbonates are formed in solution near mineral surfaces. Accomplishing these tasks will enable us to understand how such nanoparticles form, for example, the important amorphous calcium carbonate relevant to biomineralization, using bottom-up and top-down approaches. It will also provide insights into the role of waters of hydration on such processes at the microscopic level. The calculated spectroscopic properties provide a direct connection to experimental measurements being conducted by other EMSL users as well as providing a means to validate the predictions. A team of researchers from a US university, a Chinese academic institute, and PNNL with direct and close ties to experimental efforts will address these problems using appropriate computational methods. The proposed computational work is being done in close collaboration with experimental teams, a number of which use EMSL resources or are located in the EMSL. The effort falls within the EMSL Environmental Sciences Area in the solvent-mediated interfacial chemistry focus group ("Understand mineral surface complexation/associations, redox reactions, nanoparticle and colloid formation, and their impact on the reactivity, fate, and transport of anthropogenic contaminants in terrestrial and subsurface ecosystems"), and the BER High Level Grand Challenges in Biogeochemistry and Data-model Integration.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2019-10-01
End Date
2021-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Chen M., A. Mcneill, Y. Hu, and D.A. Dixon. 2020. "Elucidation of Bottom-up Growth of CaCO3 Involving Prenucleation Clusters from Structure Predictions and Decomposition of Globally Optimized (CaCO3)n Nanoclusters." ACS Nano 14, no. 4:4153-4165. PNNL-SA-152710. doi:10.1021/acsnano.9b08907
Hu Y., M. Vasiliu, S. Thanthiriwatte, V.E. Jackson, A.M. Chaka, and D.A. Dixon. 2020. "Thermodynamics of Metal Carbonates and Bicarbonates and Their Hydrates for Mg, Ca, Fe, and Cd Relevant to Mineral Energetics." Journal of Physical Chemistry A 124, no. 9:1829-1840. PNNL-SA-150219. doi:10.1021/acs.jpca.9b11741
Mcneill A.S., B. Dallas, J. Eiler, E.J. Bylaska, and D.A. Dixon. 2020. "Reaction Energetics and 13C Fractionation of Alanine Transamination in the Aqueous and Gas Phase." Journal of Physical Chemistry A 124, no. 10:2077-2089. PNNL-SA-150162. doi:10.1021/acs.jpca.9b11783