Fetisov, Evgenii2018-05-082018-05-082018-03https://hdl.handle.net/11299/196437University of Minnesota PhD dissertation. March 2018. Major: Chemistry. Advisor: J. Ilja Siepmann. 1 computer file (PDF); ix, 122 pages.redictive modeling of fluid phase and sorption equilibria for reacting systems presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions representing the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. This thesis showcases some of my efforts in developing and applying advanced simulation methods to a variety of important systems. Chapters 2 and 3 describe how a novel Monte Carlo method (reactive first principles Monte Carlo or RxFPMC) can be used to overcome some limitations of existing methods for simulation of reactive systems. Chapter 4 shows how advanced sampling techniques in combination with sophisticated interatomic potentials can be used to elucidate nucleation pathways. Chapters 5 and 6 manifest how first principles simulations can be leveraged to understand liquid structure of novel complex solvents as well as reactive processes in such solvents. Finally, the last chapter discusses the use of smart sampling algorithms to study chemisorption of mixed ligands on nanoparticles.enComputational chemistryPhysical chemistryDensity functional theoryMolecular dynamicsMolecular simulationsMonte CarloReactive equilibriaThesis or Dissertation