Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes

Understanding the origin of potential shifts in concentrated electrolytes is crucial for the design of stable and high-energy-density lithium–metal batteries. In our previous work, we identified a strong correlation between experimental electrode potential and Li<sup>+</sup>–anion intera...

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Main Author: Yumika Yokoyama (18422218) (author)
Other Authors: Kou Nakamura (22482178) (author), Naoto Tanibata (4108045) (author), Hayami Takeda (4543633) (author), Masayuki Karasuyama (9925685) (author), Ryo Kobayashi (341637) (author), Norio Takenaka (1426843) (author), Atsuo Yamada (795150) (author), Masanobu Nakayama (1417912) (author)
Published: 2025
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_version_ 1852014715827388416
author Yumika Yokoyama (18422218)
author2 Kou Nakamura (22482178)
Naoto Tanibata (4108045)
Hayami Takeda (4543633)
Masayuki Karasuyama (9925685)
Ryo Kobayashi (341637)
Norio Takenaka (1426843)
Atsuo Yamada (795150)
Masanobu Nakayama (1417912)
author2_role author
author
author
author
author
author
author
author
author_facet Yumika Yokoyama (18422218)
Kou Nakamura (22482178)
Naoto Tanibata (4108045)
Hayami Takeda (4543633)
Masayuki Karasuyama (9925685)
Ryo Kobayashi (341637)
Norio Takenaka (1426843)
Atsuo Yamada (795150)
Masanobu Nakayama (1417912)
author_role author
dc.creator.none.fl_str_mv Yumika Yokoyama (18422218)
Kou Nakamura (22482178)
Naoto Tanibata (4108045)
Hayami Takeda (4543633)
Masayuki Karasuyama (9925685)
Ryo Kobayashi (341637)
Norio Takenaka (1426843)
Atsuo Yamada (795150)
Masanobu Nakayama (1417912)
dc.date.none.fl_str_mv 2025-11-19T16:36:13Z
dc.identifier.none.fl_str_mv 10.1021/acs.jpcb.5c06002.s002
dc.relation.none.fl_str_mv https://figshare.com/articles/dataset/Causal_Relationship_between_Potential_Shift_and_Molecular_Structure_in_Concentrated_Electrolytes/30657723
dc.rights.none.fl_str_mv CC BY-NC 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Biophysics
Biochemistry
Molecular Biology
Cancer
Computational Biology
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
various solvent molecules
select reduced sets
radial distribution functions
phase madelung interaction
mitigate overfitting due
g ., homo
dominant factor governing
molecular dynamics simulations
intrinsic molecular properties
gaussian acyclic model
direct causal effect
experimental electrode potential
highly concentrated electrolytes
concentrated electrolytes understanding
intermolecular descriptors derived
lingam analysis revealed
high descriptor dimensionality
causal discovery methods
range ndf descriptors
concentrated electrolytes
causal discovery
molecular structure
based model
causal relationships
causal relationship
potential shifts
potential shift
descriptors associated
strong correlation
previous work
linear non
genetic algorithm
especially long
data set
comprehensive set
dc.title.none.fl_str_mv Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
dc.type.none.fl_str_mv Dataset
info:eu-repo/semantics/publishedVersion
dataset
description Understanding the origin of potential shifts in concentrated electrolytes is crucial for the design of stable and high-energy-density lithium–metal batteries. In our previous work, we identified a strong correlation between experimental electrode potential and Li<sup>+</sup>–anion interactions, suggesting the importance of intermolecular structure beyond conventional molecular properties. In this study, we revisit this issue from the perspective of causal discovery. We applied the Linear Non-Gaussian Acyclic Model (LiNGAM) to a data set of 75 electrolyte solutions containing LiFSI salt and various solvent molecules, using a comprehensive set of 132 descriptors including molecular properties (e.g., HOMO, LUMO, binding energy) and intermolecular descriptors derived from radial distribution functions (RDF) and their integrals (NDF) from molecular dynamics simulations. To mitigate overfitting due to high descriptor dimensionality, we employed a genetic algorithm to select reduced sets of descriptors. LiNGAM analysis revealed that descriptors associated with Li<sup>+</sup>–anion spatial distribution, especially long-range NDF descriptors, exhibit a direct causal effect with experimentally measured potential values. In contrast, no such causal relationships were identified for intrinsic molecular properties. These findings further support the recently proposed advanced theoretical framework, which incorporates a Debye–Hückel-based model and identifies the liquid-phase Madelung interaction as a dominant factor governing the potential shift in highly concentrated electrolytes. Moreover, we demonstrate that causal discovery methods can reveal fundamental physical mechanisms underlying electrochemical behavior.
eu_rights_str_mv openAccess
id Manara_e744dfc4eb4bf402ca7f899b1bf71a8b
identifier_str_mv 10.1021/acs.jpcb.5c06002.s002
network_acronym_str Manara
network_name_str ManaraRepo
oai_identifier_str oai:figshare.com:article/30657723
publishDate 2025
repository.mail.fl_str_mv
repository.name.fl_str_mv
repository_id_str
rights_invalid_str_mv CC BY-NC 4.0
spelling Causal Relationship between Potential Shift and Molecular Structure in Concentrated ElectrolytesYumika Yokoyama (18422218)Kou Nakamura (22482178)Naoto Tanibata (4108045)Hayami Takeda (4543633)Masayuki Karasuyama (9925685)Ryo Kobayashi (341637)Norio Takenaka (1426843)Atsuo Yamada (795150)Masanobu Nakayama (1417912)BiophysicsBiochemistryMolecular BiologyCancerComputational BiologyEnvironmental Sciences not elsewhere classifiedBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedvarious solvent moleculesselect reduced setsradial distribution functionsphase madelung interactionmitigate overfitting dueg ., homodominant factor governingmolecular dynamics simulationsintrinsic molecular propertiesgaussian acyclic modeldirect causal effectexperimental electrode potentialhighly concentrated electrolytesconcentrated electrolytes understandingintermolecular descriptors derivedlingam analysis revealedhigh descriptor dimensionalitycausal discovery methodsrange ndf descriptorsconcentrated electrolytescausal discoverymolecular structurebased modelcausal relationshipscausal relationshippotential shiftspotential shiftdescriptors associatedstrong correlationprevious worklinear nongenetic algorithmespecially longdata setcomprehensive setUnderstanding the origin of potential shifts in concentrated electrolytes is crucial for the design of stable and high-energy-density lithium–metal batteries. In our previous work, we identified a strong correlation between experimental electrode potential and Li<sup>+</sup>–anion interactions, suggesting the importance of intermolecular structure beyond conventional molecular properties. In this study, we revisit this issue from the perspective of causal discovery. We applied the Linear Non-Gaussian Acyclic Model (LiNGAM) to a data set of 75 electrolyte solutions containing LiFSI salt and various solvent molecules, using a comprehensive set of 132 descriptors including molecular properties (e.g., HOMO, LUMO, binding energy) and intermolecular descriptors derived from radial distribution functions (RDF) and their integrals (NDF) from molecular dynamics simulations. To mitigate overfitting due to high descriptor dimensionality, we employed a genetic algorithm to select reduced sets of descriptors. LiNGAM analysis revealed that descriptors associated with Li<sup>+</sup>–anion spatial distribution, especially long-range NDF descriptors, exhibit a direct causal effect with experimentally measured potential values. In contrast, no such causal relationships were identified for intrinsic molecular properties. These findings further support the recently proposed advanced theoretical framework, which incorporates a Debye–Hückel-based model and identifies the liquid-phase Madelung interaction as a dominant factor governing the potential shift in highly concentrated electrolytes. Moreover, we demonstrate that causal discovery methods can reveal fundamental physical mechanisms underlying electrochemical behavior.2025-11-19T16:36:13ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.jpcb.5c06002.s002https://figshare.com/articles/dataset/Causal_Relationship_between_Potential_Shift_and_Molecular_Structure_in_Concentrated_Electrolytes/30657723CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/306577232025-11-19T16:36:13Z
spellingShingle Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
Yumika Yokoyama (18422218)
Biophysics
Biochemistry
Molecular Biology
Cancer
Computational Biology
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
various solvent molecules
select reduced sets
radial distribution functions
phase madelung interaction
mitigate overfitting due
g ., homo
dominant factor governing
molecular dynamics simulations
intrinsic molecular properties
gaussian acyclic model
direct causal effect
experimental electrode potential
highly concentrated electrolytes
concentrated electrolytes understanding
intermolecular descriptors derived
lingam analysis revealed
high descriptor dimensionality
causal discovery methods
range ndf descriptors
concentrated electrolytes
causal discovery
molecular structure
based model
causal relationships
causal relationship
potential shifts
potential shift
descriptors associated
strong correlation
previous work
linear non
genetic algorithm
especially long
data set
comprehensive set
status_str publishedVersion
title Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
title_full Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
title_fullStr Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
title_full_unstemmed Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
title_short Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
title_sort Causal Relationship between Potential Shift and Molecular Structure in Concentrated Electrolytes
topic Biophysics
Biochemistry
Molecular Biology
Cancer
Computational Biology
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
various solvent molecules
select reduced sets
radial distribution functions
phase madelung interaction
mitigate overfitting due
g ., homo
dominant factor governing
molecular dynamics simulations
intrinsic molecular properties
gaussian acyclic model
direct causal effect
experimental electrode potential
highly concentrated electrolytes
concentrated electrolytes understanding
intermolecular descriptors derived
lingam analysis revealed
high descriptor dimensionality
causal discovery methods
range ndf descriptors
concentrated electrolytes
causal discovery
molecular structure
based model
causal relationships
causal relationship
potential shifts
potential shift
descriptors associated
strong correlation
previous work
linear non
genetic algorithm
especially long
data set
comprehensive set