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Path-Integral and Coarse-Graining Strategies for Complex Molecular Phenomena


Webb, Michael Anthony (2016) Path-Integral and Coarse-Graining Strategies for Complex Molecular Phenomena. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z90Z7172.


Molecular simulation provides a powerful tool for connecting molecular-level processes to physical observables. However, the facility to make those connections relies upon the application and development of theoretical methods that permit appropriate descriptions of the systems or processes to be studied. In this thesis, we utilize molecular simulation to study and predict two phenomena with very different theoretical challenges, beginning with (1) lithium-ion transport behavior in polymers and following with (2) equilibrium isotope effects with relevance to position-specific and clumped isotope studies. In the case of ion transport in polymers, there is motivation to use molecular simulation to provide guidance in polymer electrolyte design, but the length and timescales relevant for ion diffusion in polymers preclude the use of direct molecular dynamics simulation to compute ion diffusivities in more than a handful of candidate systems. In the case of equilibrium isotope effects, the thermodynamic driving forces for isotopic fractionation are often fundamentally quantum mechanical in nature, and the high precision of experimental instruments demands correspondingly accurate theoretical approaches. Herein, we describe respectively coarse-graining and path-integral strategies to address outstanding questions in these two subject areas.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Polymer; lithium-ion; batteries; isotope geochemistry; path-integral; isotopic clumping; isotope effects; molecular simulation; molecular dynamics
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemical Engineering
Awards:The Herbert Newby Mccoy Award, 2016
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Miller, Thomas F.
Group:Resnick Sustainability Institute
Thesis Committee:
  • Miller, Thomas F. (chair)
  • Wang, Zhen-Gang
  • Brady, John F.
  • Eiler, John M.
Defense Date:27 May 2016
Non-Caltech Author Email:xmwebb (AT)
Record Number:CaltechTHESIS:05252016-213050706
Persistent URL:
Webb, Michael Anthony0000-0002-7420-4474
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9761
Deposited By: Michael Webb
Deposited On:31 May 2016 20:58
Last Modified:04 Oct 2019 00:13

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