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Title: Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water

Abstract

We study NaCl ion-pair dissociation in a dilute aqueous solution using computer simulations both for the full system with long-range Coulomb interactions and for a well-chosen reference system with short-range intermolecular interactions. Analyzing results using concepts from Local Molecular Field (LMF) theory and the recently proposed AI-based analysis tool “State predictive information bottleneck” (SPIB), we show that the system with short-range interactions can accurately reproduce the transition rate for the dissociation process, the dynamics for moving between the underlying metastable states, and the transition state ensemble. Contributions from long-range interactions can be largely neglected for these processes because long-range forces from the direct interionic Coulomb interactions are almost completely canceled (>90%) by those from solvent interactions over the length scale where the transition takes place. Thus, for this important monovalent ion-pair system, short-range forces alone are able to capture detailed consequences of the collective solvent motion, allowing the use of physically suggestive and computationally efficient short-range models for the dissociation event. Here, we believe that the framework here should be applicable to disentangling mechanisms for more complex processes such as multivalent ion disassociation, where previous work has suggested that long-range contributions may be more important.

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. University of Maryland, College Park, MD (United States)
Publication Date:
Research Org.:
Univ. of Maryland, College Park, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Extreme Science and Engineering Discovery Environment (XSEDE); National Science Foundation (NSF)
OSTI Identifier:
1991198
Grant/Contract Number:  
SC0021009; CHE180027P; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B
Additional Journal Information:
Journal Volume: 126; Journal Issue: 2; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dissociation; Ions; Solvents; Stability; Transition states

Citation Formats

Wang, Dedi, Zhao, Renjie, Weeks, John D., and Tiwary, Pratyush. Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water. United States: N. p., 2022. Web. doi:10.1021/acs.jpcb.1c09454.
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Wang, Dedi, Zhao, Renjie, Weeks, John D., & Tiwary, Pratyush. Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water. United States. https://doi.org/10.1021/acs.jpcb.1c09454
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Wang, Dedi, Zhao, Renjie, Weeks, John D., and Tiwary, Pratyush. Wed . "Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water". United States. https://doi.org/10.1021/acs.jpcb.1c09454. https://www.osti.gov/servlets/purl/1991198.
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@article{osti_1991198,
title = {Influence of Long-Range Forces on the Transition States and Dynamics of NaCl Ion-Pair Dissociation in Water},
author = {Wang, Dedi and Zhao, Renjie and Weeks, John D. and Tiwary, Pratyush},
abstractNote = {We study NaCl ion-pair dissociation in a dilute aqueous solution using computer simulations both for the full system with long-range Coulomb interactions and for a well-chosen reference system with short-range intermolecular interactions. Analyzing results using concepts from Local Molecular Field (LMF) theory and the recently proposed AI-based analysis tool “State predictive information bottleneck” (SPIB), we show that the system with short-range interactions can accurately reproduce the transition rate for the dissociation process, the dynamics for moving between the underlying metastable states, and the transition state ensemble. Contributions from long-range interactions can be largely neglected for these processes because long-range forces from the direct interionic Coulomb interactions are almost completely canceled (>90%) by those from solvent interactions over the length scale where the transition takes place. Thus, for this important monovalent ion-pair system, short-range forces alone are able to capture detailed consequences of the collective solvent motion, allowing the use of physically suggestive and computationally efficient short-range models for the dissociation event. Here, we believe that the framework here should be applicable to disentangling mechanisms for more complex processes such as multivalent ion disassociation, where previous work has suggested that long-range contributions may be more important.},
doi = {10.1021/acs.jpcb.1c09454},
journal = {Journal of Physical Chemistry. B},
number = 2,
volume = 126,
place = {United States},
year = {Wed Jan 05 00:00:00 EST 2022},
month = {Wed Jan 05 00:00:00 EST 2022}
}
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https://doi.org/10.1021/acs.jpcb.1c09454
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