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Here, cation transport in poly(ethylene oxide) (PEO) and poly(ethylene carbonate) (PEC) electrolytes is investigated using atomistic molecular dynamics simulations combined with quantum mechanical calculations of representative first-shell coordination motifs. Across 14 PEO-based formulations, Na+ exhibits higher mobility than Li+, associated with a more diffuse and dynamically labile coordination environment, whereas Li+ preferentially occupies compact, long-lived, high-coordination states. Four PEC-based systems assess how matrix rigidity modulates the relationship between local coordination energetics and long-range transport. We introduce a population-weighted energetic descriptor, \u27e8Eint\u27e9, constructed from Boltzmann-averaged interaction energies and MD-derived coordination-state populations. The descriptor captures variations in the cationic contribution to conductivity, \u03c3t+, within PEO, while PEC reveals the additional influence of polymer dynamics. Within the predominantly polymer-mediated regime examined here, anion participation can stabilize persistent coordination states associated with reduced cation mobility. A reduced representation based on dominant coordination states retains the principal PEO transport relationship, highlighting the importance of state-specific populations and interaction energies rather than average coordination properties while emphasizing limits to cross-family descriptor transferability.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c04246","type":"journal-article","created":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T06:01:28Z","timestamp":1790920888000},"page":"11011-11023","source":"Crossref","is-referenced-by-count":0,"title":["Population-Weighted\nFirst-Shell Coordination States\nRationalize Li\n                    <b>+<\/b>\n                    and Na\n                    <b>+<\/b>\n                    Mobility in PEO and PEC Polymer Electrolytes"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7107-227X","authenticated-orcid":true,"given":"Gabriela","family":"Campos-Ferna\u0301ndez","sequence":"first","affiliation":[{"name":"Universidad Andre\u0301s Bello , , Repu\u0301blica 275 , ,","place":["Santiago, Chile, 8370146"]},{"name":"Universidad Andre\u0301s Bello , , ,","place":["Santiago, Chile, 8370035"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6920-703X","authenticated-orcid":true,"given":"Patricia","family":"Pe\u0301rez","sequence":"additional","affiliation":[{"name":"Universidad San Sebastia\u0301n , , Av. Del Co\u0301ndor 720, Campus Ciudad Universitaria, Ciudad Empresarial , Huechuraba, ,","place":["Santiago, Chile, 8580704"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6857-3575","authenticated-orcid":true,"given":"Fernando","family":"Gonza\u0301lez-Nilo","sequence":"additional","affiliation":[{"name":"Universidad Andre\u0301s Bello , , ,","place":["Santiago, Chile, 8370035"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9200-9859","authenticated-orcid":true,"given":"Eduardo","family":"Chamorro","sequence":"additional","affiliation":[{"name":"Universidad San Sebastia\u0301n , , Av. Del Co\u0301ndor 720, Campus Ciudad Universitaria, Ciudad Empresarial , Huechuraba, ,","place":["Santiago, Chile, 8580704"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,2]]},"reference":[{"key":"2026101508071330400_cit1","doi-asserted-by":"publisher","first-page":"217791","DOI":"10.1016\/j.ccr.2026.217791","article-title":"Molecular Design of Intrinsically Safe and Stable Electrolytes\nfor Lithium-Ion Batteries","volume":"558","author":"Ullah","year":"2026","journal-title":"Coord. Chem. 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Non-Cryst.\nSolids"},{"key":"2026101508071330400_cit4","doi-asserted-by":"publisher","first-page":"103063","DOI":"10.1016\/j.ensm.2023.103063","article-title":"Beyond\nLithium-Ion Batteries: Recent Developments in Polymer-Based Electrolytes\nfor Alternative Metal-Ion-Batteries","volume":"65","author":"Elbinger","year":"2024","journal-title":"Energy\nStorage Mater."},{"issue":"6","key":"2026101508071330400_cit5","doi-asserted-by":"publisher","first-page":"2142","DOI":"10.1021\/ma802502u","article-title":"Effect of LiClO4 on the Structure and Mobility\nof PEO-Based Solid Polymer Electrolytes","volume":"42","author":"Fullerton-Shirey","year":"2009","journal-title":"Macromolecules"},{"issue":"1\u20132","key":"2026101508071330400_cit6","doi-asserted-by":"publisher","first-page":"71","DOI":"10.1016\/j.tca.2009.10.005","article-title":"Kinetic Analysis\nof Thermal Degradation of Poly(Ethylene Glycol) and Poly(Ethylene\nOxide)s of Different Molecular Weight","volume":"498","author":"Vrandec\u030cic\u0301","year":"2010","journal-title":"Thermochim.\nActa"},{"key":"2026101508071330400_cit7","doi-asserted-by":"publisher","first-page":"124","DOI":"10.1016\/j.electacta.2015.03.228","article-title":"Characterization of NaX (X: TFSI,\nFSI) \u2013 PEO\nBased Solid Polymer Electrolytes for Sodium Batteries","volume":"175","author":"Boschin","year":"2015","journal-title":"Electrochim. 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Polym. Mater."},{"key":"2026101508071330400_cit22","doi-asserted-by":"publisher","first-page":"10","DOI":"10.1016\/j.ensm.2020.11.030","article-title":"Polymer\nElectrolytes for Sodium-Ion Batteries","volume":"36","author":"Gebert","year":"2021","journal-title":"Energy\nStorage Mater."},{"issue":"5","key":"2026101508071330400_cit23","doi-asserted-by":"publisher","first-page":"1075","DOI":"10.1039\/C7EE00524E","article-title":"Electrolyte Design Strategies and\nResearch Progress for Room-Temperature Sodium-Ion Batteries","volume":"10","author":"Che","year":"2017","journal-title":"Energy Environ. Sci."},{"issue":"7","key":"2026101508071330400_cit24","doi-asserted-by":"publisher","first-page":"4682","DOI":"10.1021\/acsapm.5c04495","article-title":"Role of Ion\nInteractions in Molecular Design Rules for Li+ and Na+ Solid Polymer Electrolytes","volume":"8","author":"Campos-Ferna\u0301ndez","year":"2026","journal-title":"ACS Appl.\nPolym. Mater."},{"issue":"8","key":"2026101508071330400_cit25","doi-asserted-by":"publisher","first-page":"4808","DOI":"10.1021\/acsomega.7b00964","article-title":"Structure-Property Relationships of Poly(Ethylene Carbonate)\nand Poly(Propylene Carbonate)","volume":"2","author":"Sasanuma","year":"2017","journal-title":"ACS Omega"},{"issue":"5","key":"2026101508071330400_cit26","doi-asserted-by":"publisher","first-page":"1575","DOI":"10.1002\/app.1974.070180525","article-title":"Poly(Ethylene Carbonate) and Poly(Propylene Carbonate):\nTransitions and Thermomechanical Spectra","volume":"18","author":"Udipi","year":"1974","journal-title":"J.\nAppl. Polym. 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A Basis Set for Correlated Wave Functions","volume":"72","author":"Krishnan","year":"1980","journal-title":"J. Chem. Phys."},{"issue":"8","key":"2026101508071330400_cit42","doi-asserted-by":"publisher","first-page":"5392","DOI":"10.1021\/acs.jctc.1c00401","article-title":"Assessment of the\nAccuracy of DFT-Predicted Li+\u2013Nucleic\nBinding Energies","volume":"17","author":"Boychuk","year":"2021","journal-title":"J. Chem. Theory Comput."},{"issue":"22","key":"2026101508071330400_cit43","doi-asserted-by":"publisher","first-page":"8373","DOI":"10.1021\/ma0490404","article-title":"Influence of Sample History on the\nMorphology and Transport Properties of PEO\u2013Lithium Salt Complexes","volume":"37","author":"Volel","year":"2004","journal-title":"Macromolecules"}],"container-title":["The Journal of Physical\nChemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.6c04246","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/41\/11011\/68732047\/acs.jpcb.6c04246.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/41\/11011\/68732047\/acs.jpcb.6c04246.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T12:20:41Z","timestamp":1792066841000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/130\/41\/11011\/5443692\/Population-Weighted-First-Shell-Coordination"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,2]]},"references-count":43,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,2]]},"published-print":{"date-parts":[[2026,10,15]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.6c04246","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,2]]}}}