{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T11:14:40Z","timestamp":1753874080430,"version":"3.41.2"},"reference-count":74,"publisher":"AIP Publishing","issue":"23","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2020,12,21]]},"abstract":"<jats:p>In dilute electrolytes, we calculate the pair correlation functions among the solvent polarization p, the solvent density n1, the cation density n2, and the anion density n3. We set up a simple Ginzburg\u2013Landau free energy for these variables, so our results are valid at distances longer than the molecular size \u03c3. In particular, we reproduce the H\u00f8ye\u2013Stell result for the polarization correlation \u27e8p\u03b1(r)p\u03b2(0)\u27e9 (\u03b1, \u03b2 = x, y, z) [J. S. H\u00f8ye and G. Stell, J. Chem. Phys. 68, 4145 (1978)], which is proportional to the second derivative \u22022(e\u2212\u03bar\/r)\/\u2202x\u03b1\u2202x\u03b2 for r \u226b \u03c3 with \u03ba being the Debye wave number. We also show that size asymmetry between the cations and the anions gives rise to similar long-range correlations in \u27e8p\u03b1(r)\u03b4n1(0)\u27e9 and \u27e8\u03b4ni(r)\u03b4n1(0)\u27e9 (i = 1, 2, 3). Moreover, we calculate the polarization time-correlation function. As a unique feature in dynamics, the longitudinal polarization fluctuations (\u221d\u2207 \u00b7 p) consist of rapidly decaying and slowly decaying components, where the latter relax with the charge density \u03c1. As a result, the long-range part of the equal-time polarization correlation changes into a different long-ranged and long-lived form after the shorter polarization relaxation.<\/jats:p>","DOI":"10.1063\/5.0030763","type":"journal-article","created":{"date-parts":[[2020,12,15]],"date-time":"2020-12-15T11:14:56Z","timestamp":1608030896000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":3,"title":["Long-range correlations of polarization and number densities in dilute electrolytes"],"prefix":"10.1063","volume":"153","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3281-3562","authenticated-orcid":false,"given":"Akira","family":"Onuki","sequence":"first","affiliation":[{"name":"Department of Physics, Kyoto University , Kyoto 606-8502, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2020,12,15]]},"reference":[{"volume-title":"Intermolecular and Surface Forces","year":"1991","key":"2023062603422378700_c1"},{"key":"2023062603422378700_c2","first-page":"185","article-title":"The theory of electrolytes. I. Freezing point depression and related phenomena","volume":"24","year":"1923","journal-title":"Phys. Z."},{"key":"2023062603422378700_c3","doi-asserted-by":"publisher","first-page":"020201(R)","DOI":"10.1103\/physrevb.72.020201","article-title":"Slow polarization relaxation in water observed by hyper-Rayleigh scattering","volume":"72","year":"2005","journal-title":"Phys. Rev. B"},{"key":"2023062603422378700_c4","doi-asserted-by":"publisher","first-page":"114501","DOI":"10.1063\/1.3089882","article-title":"Electric field of Ions in solution probed by hyper-Rayleigh scattering","volume":"130","year":"2009","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c5","doi-asserted-by":"publisher","first-page":"134503","DOI":"10.1063\/1.4931973","article-title":"Long-range orientation correlation in dipolar liquids probed by hyper-Rayleigh scattering","volume":"143","year":"2015","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c6","doi-asserted-by":"publisher","first-page":"214505","DOI":"10.1063\/1.4998589","article-title":"Water-water correlations in electrolyte solutions probed by hyper-Rayleigh scattering","volume":"147","year":"2017","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c8","doi-asserted-by":"publisher","first-page":"e1501891","DOI":"10.1126\/sciadv.1501891","article-title":"Electrolytes induce long-range orientational order and free energy changes in the H-bond network of bulk water","volume":"2","year":"2016","journal-title":"Sci. Adv."},{"key":"2023062603422378700_c9","doi-asserted-by":"publisher","first-page":"4311","DOI":"10.1021\/acs.jpclett.6b01851","article-title":"Second-harmonic scattering as a probe of structural correlations in liquids","volume":"7","year":"2016","journal-title":"J. Phys. Chem. Lett."},{"key":"2023062603422378700_c10","doi-asserted-by":"publisher","first-page":"263001","DOI":"10.1103\/physrevlett.120.263001","article-title":"Salt-induced long-to-short range orientational transition in water","volume":"120","year":"2018","journal-title":"Phys. Rev. Lett."},{"key":"2023062603422378700_c11","doi-asserted-by":"publisher","first-page":"104502","DOI":"10.1063\/1.4943097","article-title":"Effect of simple solutes on the long range dipolar correlations in liquid water","volume":"144","year":"2016","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c12","doi-asserted-by":"publisher","first-page":"181103","DOI":"10.1063\/1.4983221","article-title":"Communication: Mean-field theory of water-water correlations in electrolyte solutions","volume":"146","year":"2017","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c13","doi-asserted-by":"publisher","first-page":"2031","DOI":"10.1021\/acs.jpclett.7b00727","article-title":"Size and origins of long-range orientational water correlations in dilute aqueous salt solutions","volume":"8","year":"2017","journal-title":"J. Phys. Chem. Lett."},{"key":"2023062603422378700_c14","doi-asserted-by":"publisher","first-page":"1985","DOI":"10.1021\/acs.jpclett.8b00606","article-title":"Screened Coulombic orientational correlations in dilute aqueous electrolytes","volume":"9","year":"2018","journal-title":"J. Phys. Chem. Lett."},{"key":"2023062603422378700_c15","doi-asserted-by":"publisher","first-page":"3698","DOI":"10.1021\/acs.jpclett.8b01690","article-title":"What does second-harmonic scattering measure in diluted electrolytes ?","volume":"9","year":"2018","journal-title":"J. Phys. Chem. Lett."},{"key":"2023062603422378700_c16","doi-asserted-by":"publisher","first-page":"064501","DOI":"10.1063\/1.5133753","article-title":"Ion pair correlations due to interference between solvent polarizations induced in water","volume":"152","year":"2020","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c17a","doi-asserted-by":"publisher","first-page":"4145","DOI":"10.1063\/1.436275","article-title":"Ionic solution in a molecular polar solvent","volume":"68","year":"1978","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c17b","doi-asserted-by":"publisher","first-page":"1985","DOI":"10.1063\/1.438519","article-title":"Correlation functions for an ionic solution in a polar solvent","volume":"71","author":"Hphiye","year":"1979","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c18","doi-asserted-by":"publisher","first-page":"305","DOI":"10.1016\/0375-9601(68)90664-6","article-title":"The form of the Bogoliubov condition of weakening of correlation in classical fluids with the van der Waals and dipole\u2013dipole interactions of molecules at large distances","volume":"26","year":"1968","journal-title":"Phys. Lett. A"},{"key":"2023062603422378700_c19","doi-asserted-by":"publisher","first-page":"2703","DOI":"10.1063\/1.1681431","article-title":"Space and time dependent polarization fluctuations in dielectric media","volume":"60","year":"1974","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c20","doi-asserted-by":"publisher","first-page":"493","DOI":"10.1063\/1.434895","article-title":"Fluctuations of polarization and magnetization in dielectric and magnetic media","volume":"67","year":"1977","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c21","doi-asserted-by":"publisher","first-page":"572","DOI":"10.1016\/0378-4371(79)90033-5","article-title":"Fluctuation theories for dielectrics","volume":"95","year":"1979","journal-title":"Physica A"},{"key":"2023062603422378700_c22","doi-asserted-by":"publisher","first-page":"3095","DOI":"10.1063\/1.436149","article-title":"Dipole correlations in conducting media","volume":"68","year":"1978","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c23","doi-asserted-by":"publisher","first-page":"3323","DOI":"10.1103\/physrevb.8.3323","article-title":"Critical behavior of magnets with dipolar interactions. I. Renormarization group near four dimensions","volume":"8","year":"1973","journal-title":"Phys. Rev. B"},{"key":"2023062603422378700_c24","doi-asserted-by":"publisher","first-page":"021201","DOI":"10.1103\/physreve.81.021201","article-title":"Long distance correlations in molecular orientations of liquid water and shape dependant hydrophobic force","volume":"81","year":"2010","journal-title":"Phys. Rev. E"},{"key":"2023062603422378700_c25","doi-asserted-by":"publisher","first-page":"041103","DOI":"10.1063\/1.4817321","article-title":"Communication: Long-range angular correlations in liquid water","volume":"139","year":"2013","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c26","doi-asserted-by":"publisher","first-page":"194503","DOI":"10.1063\/1.5005581","article-title":"Long-range dipolar order and dispersion forces in polar liquids","volume":"147","year":"2017","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c27","doi-asserted-by":"publisher","first-page":"154503","DOI":"10.1063\/1.4932972","article-title":"Fluctuations of local electric field and dipole moments in water between metal walls","volume":"143","year":"2015","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c28","doi-asserted-by":"publisher","first-page":"014501","DOI":"10.1063\/1.5037673","article-title":"Theory of nonionic hydrophobic solutes in mixture solvent: Solvent-mediated interaction and solute-induced phase separation","volume":"149","year":"2018","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c29","doi-asserted-by":"publisher","first-page":"074503","DOI":"10.1063\/5.0015446","article-title":"Theory of electrolytes including steric, attractive, and hydration interactions","volume":"153","year":"2020","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c30a","doi-asserted-by":"publisher","first-page":"562","DOI":"10.1021\/je60047a029","article-title":"Apparent molal volumes of aqueous sodium tetraphenylboron solutions from 0.deg. to 60.deg","volume":"15","year":"1970","journal-title":"J. Chem. Eng. Data"},{"key":"2023062603422378700_c30b","doi-asserted-by":"publisher","first-page":"147","DOI":"10.1021\/cr60270a001","article-title":"The molal volumes of electrolytes","volume":"71","author":"Millero","year":"1971","journal-title":"Chem. Rev."},{"key":"2023062603422378700_c31a","doi-asserted-by":"publisher","first-page":"234905","DOI":"10.1063\/1.4838795","article-title":"Membrane formation by preferential solvation of ions in mixture of water, 3-methylpyridine, and sodium tetraphenylborate","volume":"139","year":"2013","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c31b","doi-asserted-by":"publisher","first-page":"59","DOI":"10.1016\/j.cocis.2016.02.007","article-title":"Structure formation due to antagonistic salts","volume":"22","year":"2016","journal-title":"Curr. Opin. Colloid Interface Sci."},{"key":"2023062603422378700_c33","doi-asserted-by":"publisher","first-page":"72","DOI":"10.1063\/1.1749611","article-title":"Molecular arrangement and x-ray diffraction in ionic solutions","volume":"3","year":"1935","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c34a","doi-asserted-by":"publisher","first-page":"6343","DOI":"10.1088\/0953-8984\/16\/36\/002","article-title":"Structure and dynamics of concentrated aqueous solutions of aluminium chloride, beryllium chloride and aluminium bromide: Raman, inelastic neutron scattering and x-ray diffraction results","volume":"16","year":"2004","journal-title":"J. Phys.: Condens. Matter"},{"key":"2023062603422378700_c34b","doi-asserted-by":"publisher","first-page":"142","DOI":"10.1016\/j.molliq.2006.12.007","article-title":"Evidence of a local order in concentrated aqueous solutions of salts constituted by ions of different valences. X-ray diffraction and Raman spectroscopy experiments","volume":"134","year":"2007","journal-title":"J. Mol. Liq."},{"key":"2023062603422378700_c35","doi-asserted-by":"publisher","first-page":"2598","DOI":"10.1021\/acs.jpclett.0c00322","article-title":"Nanometer-scale correlations in aqueous salt solutions","volume":"11","year":"2020","journal-title":"J. Phys. Chem. Lett."},{"key":"2023062603422378700_c36","doi-asserted-by":"publisher","first-page":"065604","DOI":"10.1103\/physrevmaterials.3.109902","article-title":"Local correlated motions in aqueous solution of sodium chloride","volume":"3","year":"2019","journal-title":"Phys.Rev. Mater."},{"volume-title":"Phase Transition Dynamics","year":"2002","key":"2023062603422378700_c37"},{"volume-title":"Theory of Dielectrics","year":"1949","key":"2023062603422378700_c38"},{"key":"2023062603422378700_c39","doi-asserted-by":"publisher","first-page":"405","DOI":"10.1080\/00268977500100341","article-title":"On the theory of dielectric relaxation","volume":"29","year":"1975","journal-title":"Mol. Phys."},{"key":"2023062603422378700_c40","doi-asserted-by":"publisher","first-page":"4850","DOI":"10.1063\/1.434664","article-title":"Dielectric dispersion and dielectric friction in electrolyte solutions.I.","volume":"67","year":"1977","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c41","doi-asserted-by":"publisher","first-page":"4244","DOI":"10.1021\/j100218a031","article-title":"Dielectric friction and molecular reorientation","volume":"86","year":"1982","journal-title":"J. Phys. Chem."},{"key":"2023062603422378700_c42","doi-asserted-by":"publisher","first-page":"7338","DOI":"10.1063\/1.456213","article-title":"Polarization relaxation, dielectric dispersion, and solvation dynamics in dense dipolar liquid","volume":"90","year":"1989","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c43","doi-asserted-by":"publisher","first-page":"104506","DOI":"10.1063\/1.2672734","article-title":"Are dipolar liquids ferroelectric? Simulation studies","volume":"126","year":"2007","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c44","first-page":"121","article-title":"Dispersion of the conductivity and dielectric constants of strong electrolytes","volume":"29","year":"1928","journal-title":"Phys. Z."},{"key":"2023062603422378700_c45","doi-asserted-by":"publisher","first-page":"4","DOI":"10.1103\/physrev.92.4","article-title":"Theory of ac space-charge polarization effects in photoconductors, semiconductors, and electrolytes","volume":"92","year":"1953","journal-title":"Phys. Rev."},{"key":"2023062603422378700_c46","doi-asserted-by":"publisher","first-page":"137","DOI":"10.1016\/s0927-7757(02)00379-5","article-title":"Theory of electrode polarization: Application to parallel plate cell dielectric spectroscopy experiments","volume":"210","year":"2002","journal-title":"Colloids Surf. A"},{"key":"2023062603422378700_c47","doi-asserted-by":"publisher","first-page":"021506","DOI":"10.1103\/physreve.70.021506","article-title":"Diffuse-charge dynamics in electrochemical systems","volume":"70","year":"2004","journal-title":"Phys. Rev. E"},{"key":"2023062603422378700_c48a","doi-asserted-by":"publisher","first-page":"167101","DOI":"10.1063\/1.5023579","article-title":"Comment on gWater-water correlations in electrolyte solutions probed by hyper-Rayleigh Scatteringh [J. Chem. Phys. 147, 214505 (2017)]","volume":"149","year":"2018","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c48b","doi-asserted-by":"publisher","first-page":"167102","DOI":"10.1063\/1.5043417","article-title":"Response to Comment on eWater-water correlations in electrolyte solutions probed by hyper-Rayleigh Scatteringfh [J. Chem. Phys. 149, 167101 (2018)]","volume":"149","year":"2018","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c49a","doi-asserted-by":"publisher","first-page":"966","DOI":"10.1063\/1.1742723","article-title":"On the theory of oxidation-reduction reactions involving electron transfer. I","volume":"24","year":"1956","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c49b","doi-asserted-by":"publisher","first-page":"1858","DOI":"10.1063\/1.1733886","article-title":"Free energy of nonequilibrium polarization Systems. ll. Homogeneous and electrode systems","volume":"38","author":"Marcus","year":"1963","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c50","doi-asserted-by":"publisher","first-page":"6853","DOI":"10.1063\/1.454383","article-title":"Solution reaction path Hamiltonian for reactions in polar solvents. I. Formulation","volume":"88","year":"1988","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c51a","doi-asserted-by":"publisher","first-page":"57","DOI":"10.1016\/s0009-2614(99)00455-8","article-title":"The dielectric relaxation of water between 08\u00b0C and 358\u00b0C","volume":"306","year":"1999","journal-title":"Chem. Phys. Lett."},{"key":"2023062603422378700_c51b","doi-asserted-by":"publisher","first-page":"8984","DOI":"10.1039\/b906555p","article-title":"Interactions and dynamics in electrolyte solutions by dielectric spectroscopy","volume":"11","year":"2009","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2023062603422378700_c53a","doi-asserted-by":"publisher","first-page":"467","DOI":"10.1063\/1.457481","article-title":"Molecular dynamics simulation of water between two ideal classical metal walls","volume":"91","year":"1989","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c53b","doi-asserted-by":"publisher","first-page":"423","DOI":"10.1039\/b805544k","article-title":"Water at an electrochemical interface-a simulation study","volume":"141","year":"2009","journal-title":"Faraday Discuss."},{"key":"2023062603422378700_c54","doi-asserted-by":"publisher","first-page":"102001","DOI":"10.1088\/0957-0233\/24\/10\/102001","article-title":"Electrode polarization in dielectric measurements: A review","volume":"24","year":"2013","journal-title":"Meas. Sci. Technol."},{"volume-title":"Electrochemistry","year":"2007","key":"2023062603422378700_c55"},{"key":"2023062603422378700_c56","doi-asserted-by":"publisher","first-page":"4585","DOI":"10.1021\/cr040087x","article-title":"Ion pairing","volume":"106","year":"2006","journal-title":"Chem. Rev."},{"key":"2023062603422378700_c57","doi-asserted-by":"publisher","first-page":"424102","DOI":"10.1088\/0953-8984\/21\/42\/424102","article-title":"Inflation of the screening length induced by Bjerrum pairs","volume":"21","year":"2009","journal-title":"J. Phys.: Condens. Matter"},{"key":"2023062603422378700_c58","doi-asserted-by":"publisher","first-page":"3604","DOI":"10.1103\/physreve.48.3604","article-title":"Asymptotic analysis of primitive model electrolytes and the electrical double layer","volume":"48","year":"1993","journal-title":"Phys. Rev. E"},{"key":"2023062603422378700_c59","doi-asserted-by":"publisher","first-page":"2258","DOI":"10.1063\/1.459896","article-title":"Microscopic free energy functional for polarization fluctuations: Generalization of Marcus\u2013Felderhof expression","volume":"94","year":"1991","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c60","doi-asserted-by":"publisher","first-page":"495","DOI":"10.1080\/00268970902865493","article-title":"The statistics of electric field fluctuations in liquid water","volume":"107","year":"2009","journal-title":"Mol. Phys."},{"volume-title":"Electrodynamics of Continuous Media","year":"1984","key":"2023062603422378700_c61"},{"key":"2023062603422378700_c62","doi-asserted-by":"publisher","first-page":"143","DOI":"10.1080\/00018737900101365","article-title":"The nature of the liquid-vapour interface and other topics in the statistical mechanics of non-uniform, classical fluids","volume":"28","year":"1979","journal-title":"Adv. Phys."},{"key":"2023062603422378700_c63","doi-asserted-by":"publisher","first-page":"194102","DOI":"10.1063\/1.3589142","article-title":"Molecular density functional theory of solvation: From polar solvents to water","volume":"134","year":"2011","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c64","doi-asserted-by":"publisher","first-page":"1486","DOI":"10.1021\/ja01299a050","article-title":"Electric moments of molecules in liquids","volume":"58","year":"1936","journal-title":"J. Am. Chem. Soc."},{"key":"2023062603422378700_c65","doi-asserted-by":"publisher","first-page":"911","DOI":"10.1063\/1.1750343","article-title":"The dielectric polarization of polar liquids","volume":"7","year":"1939","journal-title":"J. Chem. Phys."},{"key":"2023062603422378700_c66","doi-asserted-by":"publisher","first-page":"14003","DOI":"10.1073\/pnas.1006599107","article-title":"Small-angle scattering and the structure of ambient liquid water","volume":"107","year":"2010","journal-title":"PNAS"},{"key":"2023062603422378700_c67a","doi-asserted-by":"publisher","first-page":"453","DOI":"10.1088\/0953-8984\/17\/3\/004","article-title":"Intermediate-range order in aqueous solutions of salts: A systematic computer simulation study","volume":"17","year":"2005","journal-title":"J. Phys.: Condens. Matter"},{"key":"2023062603422378700_c67b","doi-asserted-by":"publisher","first-page":"014201","DOI":"10.1103\/PhysRevB.73.014201","article-title":"Intermediate-range order and collective dynamics in an aqueous solution of trivalent cations","volume":"73","author":"Ribeiro","year":"2006","journal-title":"Phys. Rev. B"},{"key":"2023062603422378700_c68","doi-asserted-by":"publisher","first-page":"405","DOI":"10.1103\/physrev.37.405","article-title":"Reciprocal relations in irreversible processes. I.","volume":"37","year":"1931","journal-title":"Phys. Rev."}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0030763\/15584249\/234501_1_online.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0030763\/15584249\/234501_1_online.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,6,26]],"date-time":"2023-06-26T03:42:29Z","timestamp":1687750949000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/153\/23\/234501\/199660\/Long-range-correlations-of-polarization-and-number"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,12,15]]},"references-count":74,"journal-issue":{"issue":"23","published-print":{"date-parts":[[2020,12,21]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0030763","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"type":"print","value":"0021-9606"},{"type":"electronic","value":"1089-7690"}],"subject":[],"published-other":{"date-parts":[[2020,12,21]]},"published":{"date-parts":[[2020,12,15]]},"article-number":"234501"}}