Field-Driven Simulations to Probe the Impact of Ionic Correlations on Solution Transport Coefficients in Binary, Ternary, and Reciprocal Quaternary Aqueous Electrolytes

Marioni, Nico; Rajesh, Akhila; Zhang, Zidan; Freeman, Benny D.; Ganesan, Venkat

doi:10.1021/acs.jctc.5c01341

Field-Driven Simulations to Probe the Impact of Ionic Correlations on Solution Transport Coefficients in Binary, Ternary, and Reciprocal Quaternary Aqueous Electrolytes

Journal Article · Thu Nov 20 00:00:00 EST 2025 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.5c01341· OSTI ID:3005246

^[1]; Rajesh, Akhila ^[1]; ^[1]; ^[1]; ^[1]

Univ. of Texas, Austin, TX (United States)

Ionic correlations play a critical role in governing transport properties of mixed-salt aqueous electrolyte solutions, yet their quantitative characterization remains challenging, particularly for multicomponent aqueous systems. Here, we develop a general nonequilibrium molecular dynamics framework to efficiently compute Onsager transport coefficients and ionic correlations in mixed-salt aqueous solutions. Using field-driven simulations, we obtain accurate Onsager matrices for LiCl/ KCl, KCl/KBr, and LiBr/KCl electrolyte solutions with significantly reduced computational cost relative to equilibrium Green−Kubo methods. The framework enables direct assessment of how attractive cation−anion and repulsive like-ion interactions contribute to conductivity and salt diffusivity across compositions. While static ion pairing exhibits strong composition dependence, dynamic ion correlations remain nearly invariant, leading to constant deviations from Nernst−Einstein predictions. These results highlight the disconnect between static ion association and dynamic transport correlations, and they establish a transferable approach for analyzing ion transport in complex electrolyte environments relevant to separation processes and electrochemical systems.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0019272

OSTI ID:: 3005246

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 23 Vol. 21; ISSN 1549-9626; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Field-Driven Simulations to Probe the Impact of Ionic Correlations on Solution Transport Coefficients in Binary, Ternary, and Reciprocal Quaternary Aqueous Electrolytes

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