Graduation Year

2020

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemistry

Major Professor

Brian Space, Ph.D.

Committee Member

Tom Keyes, Ph.D.

Committee Member

Arjan van der Vaart, Ph.D.

Committee Member

Shengqian Ma, Ph.D.

Committee Member

H. Lee Woodcock, Ph.D.

Keywords

gas sorption, metal-organic frameworks, molecular dyanmics, Monte Carlo, porous materials

Abstract

Theoretical modeling is extremely useful in guiding to experiment; however quantitatively accurate modeling of energy-relevant small molecule sorption at the heterogeneous interfaces present in metal-organic materials (MOMs) is currently challenging. MOMs are an emerging class of materials consisting of inorganic clusters and organic linkers that offer great potential in the areas of gas storage, gas separation, and catalysis due to the possibility of large surface areas, complex heterogeneous surfaces, and rational designability. Efficient chemical separations involving these materials could reduce the US’s total energy consumption by approximately 10 to 15%. In this dissertation, the parameterization of small molecules and metal clusters with existing potentials as well as the development of a novel next-generation potential with associated small molecule and material parameters are discussed. The resulting force-fields, denoted PHAHST, represent a significant advance in the field and can quantitatively predict/retrodict binding sites and energetics at complex heterogeneous interfaces. This is accomplished via a physically grounded approach to all potential forms, mixing rules, and parameters as well as including explicit polarization in all environments. The resulting force-fields are extensible and a procedure for developing compatible models is established. All parameters and code associated with this work are freely available online at https://github.com/mpmccode/mpmc.

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