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A hierarchical approach to accurate ...

Garrison, Stephen L.

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A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations.

Record Type:	Electronic resources : Monograph/item
Title/Author:	A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations./
Author:	Garrison, Stephen L.
Description:	332 p.
Notes:	Source: Dissertation Abstracts International, Volume: 66-03, Section: B, page: 1584.
Contained By:	Dissertation Abstracts International66-03B.
Subject:	Engineering, Chemical. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3169507
ISBN:	9780542056277

A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations.
Garrison, Stephen L.

A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations. - 332 p.

Source: Dissertation Abstracts International, Volume: 66-03, Section: B, page: 1584.

Thesis (Ph.D.)--University of Delaware, 2005.

The combination of molecular simulations and potentials obtained from quantum chemistry is shown to be able to provide reasonably accurate thermodynamic property predictions. Gibbs ensemble Monte Carlo simulations are used to understand the effects of small perturbations to various regions of the model Lennard-Jones 12-6 potential. However, when the phase behavior and second virial coefficient are scaled by the critical properties calculated for each potential, the results obey a corresponding states relation suggesting a non-uniqueness problem for interaction potentials fit to experimental phase behavior. Several variations of a procedure collectively referred to as quantum mechanical Hybrid Methods for Interaction Energies (HM-IE) are developed and used to accurately estimate interaction energies from CCSD(T) calculations with a large basis set in a computationally efficient manner for the neon-neon, acetylene-acetylene, and nitrogen-benzene systems. Using these results and methods, an ab initio, pairwise-additive, site-site potential for acetylene is determined and then improved using results from molecular simulations using this initial potential. The initial simulation results also indicate that a limited range of energies important for accurate phase behavior predictions. Second virial coefficients calculated from the improved potential indicate that one set of experimental data in the literature is likely erroneous. This prescription is then applied to methanethiol. Difficulties in modeling the effects of the lone pair electrons suggest that charges on the lone pair sites negatively impact the ability of the intermolecular potential to describe certain orientations, but that the lone pair sites may be necessary to reasonably duplicate the interaction energies for several orientations. Two possible methods for incorporating the effects of three-body interactions into simulations within the pairwise-additivity formulation are also developed. A low density approximation for the pair and three-body distribution functions is simpler to implement, but the results based on the numerical solution of the inhomogeneous Ornstein-Zernike equation using the Percus-Yevick closure are more accurate. Given the low temperatures for phase equilibria of the model system, neon, several approximations to estimate the quantum effects on the atomic nuclei are presented with reasonable success.

ISBN: 9780542056277Subjects--Topical Terms:

1018531
Engineering, Chemical.

A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations.
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100 1 $a Garrison, Stephen L. $3 1914956
245 1 2 $a A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations.
300 $a 332 p.
500 $a Source: Dissertation Abstracts International, Volume: 66-03, Section: B, page: 1584.
500 $a Professor in charge: Stanley I. Sandler.
502 $a Thesis (Ph.D.)--University of Delaware, 2005.
520 $a The combination of molecular simulations and potentials obtained from quantum chemistry is shown to be able to provide reasonably accurate thermodynamic property predictions. Gibbs ensemble Monte Carlo simulations are used to understand the effects of small perturbations to various regions of the model Lennard-Jones 12-6 potential. However, when the phase behavior and second virial coefficient are scaled by the critical properties calculated for each potential, the results obey a corresponding states relation suggesting a non-uniqueness problem for interaction potentials fit to experimental phase behavior. Several variations of a procedure collectively referred to as quantum mechanical Hybrid Methods for Interaction Energies (HM-IE) are developed and used to accurately estimate interaction energies from CCSD(T) calculations with a large basis set in a computationally efficient manner for the neon-neon, acetylene-acetylene, and nitrogen-benzene systems. Using these results and methods, an ab initio, pairwise-additive, site-site potential for acetylene is determined and then improved using results from molecular simulations using this initial potential. The initial simulation results also indicate that a limited range of energies important for accurate phase behavior predictions. Second virial coefficients calculated from the improved potential indicate that one set of experimental data in the literature is likely erroneous. This prescription is then applied to methanethiol. Difficulties in modeling the effects of the lone pair electrons suggest that charges on the lone pair sites negatively impact the ability of the intermolecular potential to describe certain orientations, but that the lone pair sites may be necessary to reasonably duplicate the interaction energies for several orientations. Two possible methods for incorporating the effects of three-body interactions into simulations within the pairwise-additivity formulation are also developed. A low density approximation for the pair and three-body distribution functions is simpler to implement, but the results based on the numerical solution of the inhomogeneous Ornstein-Zernike equation using the Percus-Yevick closure are more accurate. Given the low temperatures for phase equilibria of the model system, neon, several approximations to estimate the quantum effects on the atomic nuclei are presented with reasonable success.
590 $a School code: 0060.
650 4 $a Engineering, Chemical. $3 1018531
650 4 $a Physics, Molecular. $3 1018648
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791 $a Ph.D.
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