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Reliable Computational Studies of the Role of Metal Dications in Organic Complexation and Mineral Formation and the Formation of Atmospheric Acid Gases


EMSL Project ID
51863

Abstract

The proposed research has two major components. The first component will be to study the interaction of metal dications with organic materials, which is very important in geochemical and biogeochemical interactions. These processes are important for the formation of minerals and their dissolution, carbon dioxide capture and sequestration, biomineralization and carbon cycling. In addition, the interactions of metal dications with humic and fulvic acids play a role in in the ability of plant roots to uptake water and nutrients. We propose to use advanced computational chemistry approaches implemented on EMSL’s massively parallel computers to develop quantitative values which will lead to new understanding of the physical phenomena that occur at different spatial scales. We will use approaches that we have developed to: (1) predict reliable heats of formation of monomer species of carbonates and bicarbonates to predict cohesive energies of bulk minerals and serve as benchmarks for more approximate methods; and (2) develop and exploit high level computational methods for the prediction of the interaction of key sites in humic and fulvic acids with +II formal oxidation state cations, including the role of such cations interacting with different organic groups. The calculated energetics and 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. The second component is to study how Lewis acid gas pollutants released into the atmosphere as a result of fossil fuel combustion for energy production can be converted into Brönsted acids and higher oxides. We will use our advanced computational chemistry approaches to: (3) develop reliable potential energy surfaces for the formation of HONO and HONO2 from NO2; (4) develop reliable potential energy surfaces for the formation of SO3 and hence H2SO4, and (5) reliable potential energy surfaces for the reaction of (H2O)n with N2O5. These are important initial steps leading to aerosol formation and acid rain. Our results can be directly integrated with experimental work in the area of organic matter in the subsurface and for atmospheric chemistry including aerosol formation. The proposed work is directly relevant to topics ET1 and ET6 from the EMSL call as well as to the BER mission areas of atmospheric chemistry and aerosol formation and geochemistry/biogeochemistry interactions from organic matter. The proposed work will help to address the BER Grand Challenges to advance modeling and understanding of important ecological, biological, and carbon cycle interactions.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2021-10-01
End Date
2022-09-30
Status
Closed

Team

Principal Investigator

David Dixon
Institution
University of Alabama

Co-Investigator(s)

Joseph Francisco
Institution
University of Pennsylvania

Team Members

Gabriel de Melo
Institution
University of Alabama

Eddy Lontchi
Institution
University of Alabama

Rudradatt Persaud
Institution
University of Alabama

Zachary Lee
Institution
University of Alabama

Anne Chaka
Institution
Pacific Northwest National Laboratory

Monica Vasiliu
Institution
University of Alabama