Development of quantum chemistry-based polarizable potential to describe intermolecular interactions of nonionic polymers with water

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Title Development of quantum chemistry-based polarizable potential to describe intermolecular interactions of nonionic polymers with water
Publication Type dissertation
School or College College of Engineering
Department Materials Science & Engineering
Author Starovoytov, Oleg N.
Date 2011-05
Description A new quantum chemistry-based, atomic point polarizable dipole potential was developed for molecular dynamic (MD) simulations of poly (ethylene oxide) (PEO) and poly (propylene oxide) (PPO) aqueous solutions employing a modified version of a single water molecule with four interaction sites and Drude polarizability (SWM4-DP). A twoextended charge ether model has been chosen as best describing electrostatic potential of DME. Ether/water interactions were parameterized to reproduce the binding energy of water with 1,2-dimethoxyethane (DME) that was determined from high-level quantum chemistry calculations. The DME/water nonbonded parameters were found to be transferrable to 1,2-dimethoxypropane (DMP). An accuracy of the developed force field was justified by comparing thermodynamics properties obtained from molecular dynamics simulations with experimental data including free energy, enthalpy, and entropy of DME solvation. Free energy of DME solvation in water was obtained employing a new interface transit method (ITM) followed by calculations using perturbation theory. Simulations of DME/water solutions at room temperature using the new polarizable force field yielded enthalpy of solvation in a good agreement with experiment. Simulations of PEO/water and PPO/water solutions improved ability of the new force field to capture, at least qualitatively, low critical solution temperature (LCST) behavior in these solutions. The predicted miscibility of PEO and water as a function of temperature was found to be strongly correlated with the predicted free energy of solvation of DME in water for the various force fields investigated. Intermolecular pair correlations are employed to analyze phase behavior of nonionic polymers in aqueous solution.
Type Text
Publisher University of Utah
Subject Quantum chemistry; Polarizable potential; Intermolecular interactions; Nonionic polymers; Aqueous solutions; Molecular dynamic simulations; Poly (ethylene oxide); PEO; Poly (propylene oxide); PPO; Drude polarizability; DME; DMP
Dissertation Institution University of Utah
Dissertation Name Doctor of Philosophy
Language eng
Rights Management Copyright © Oleg N. Starovoytov 2011
Format application/pdf
Format Medium application/pdf
Format Extent 63,310,375 bytes
Identifier us-etd3,26961
Source Original housed in Marriott Library Special Collections, QC3.5 2011 .S83
ARK ark:/87278/s6qf97mw
Setname ir_etd
ID 194457
Reference URL https://collections.lib.utah.edu/ark:/87278/s6qf97mw
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