Examining the Role of Different Molecular Interactions on Activation Energies and Activation Volumes in Liquid Water

There are a large number of force fields available to model water in molecular dynamics simulations, which each have their own strengths and weaknesses in describing the behavior of the liquid. One particular weakness in many of these models is their description of dynamics away from ambient conditi...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2021-05, Vol.17 (5), p.2659-2671
Main Authors: Piskulich, Zeke A, Thompson, Ward H
Format: Article
Language:English
Subjects:
Activation energy
Dynamics
Fluctuation theory
Fluid dynamics
Molecular dynamics
Molecular interactions
Physical simulation
Pressure dependence
Temperature dependence
Water
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Summary:There are a large number of force fields available to model water in molecular dynamics simulations, which each have their own strengths and weaknesses in describing the behavior of the liquid. One particular weakness in many of these models is their description of dynamics away from ambient conditions, where their ability to reproduce measurements is mixed. To investigate this issue, we use the recently developed fluctuation theory for dynamics to directly evaluate measures of the local temperature and pressure dependence: the activation energy and the activation volume. We examine these activation parameters for hydrogen-bond jump exchange times, OH reorientation times, and diffusion coefficients calculated from the SPC/E, SPC/Fw, TIP3P-PME, TIP3P-PME/Fw, OPC3, TIP4P/2005, TIP4P/Ew, E3B2, and E3B3 water models. Activation energy decompositions available through the fluctuation theory approach provide mechanistic insight into the origins of different temperature dependences between the various models, as well as the influence of three-body effects and flexibility.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.0c01217