{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T22:24:43Z","timestamp":1787005483256,"version":"build-2736575974"},"reference-count":61,"publisher":"AIP Publishing","issue":"13","funder":[{"name":"Michigan State University Discretionary Funding Initiative"}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,10,7]]},"abstract":"<jats:p>Non-hydrogen bonding van der Waals liquids with dipole\u2013dipole interactions are typically viewed as non-associative and not considered able to sustain large supramolecular structures. Combining broadband dielectric spectroscopy (BDS) and rheology, we demonstrate the supramolecular formation in a group of non-hydrogen bonding van der Waals liquids, i.e., 1-bromo-2-ethylhexane, 1-chloro-2-ethylhexane, and 1-bromo-3,7-dimethyloctane. BDS shows an emergence of a Debye-like process slower than their structural relaxation, which follows super-Arrhenius temperature dependence. Meanwhile, rheological measurements reveal a noticeable dynamical separation between the terminal relaxation and the structural rearrangements. Interestingly, the rheological terminal time agrees remarkably well with the dielectric Debye-like relaxation time, pointing to a strong coupling between the terminal flow and the supramolecular dynamics of these van der Waals liquids. These results highlight a key role of intermolecular dipole\u2013dipole interaction in the supramolecular structure formation and the slow dynamics of van der Waals liquids.<\/jats:p>","DOI":"10.1063\/5.0284312","type":"journal-article","created":{"date-parts":[[2025,10,1]],"date-time":"2025-10-01T11:34:14Z","timestamp":1759318454000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":3,"title":["Evidence for supramolecular dynamics of non-hydrogen bonding polar van der Waals liquids"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2798-6749","authenticated-orcid":false,"given":"Shalin","family":"Patil","sequence":"first","affiliation":[{"name":"Department of Chemical Engineering and Materials Science, Michigan State University 1 , East Lansing, Michigan 48824,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8295-6433","authenticated-orcid":false,"given":"Catalin","family":"Gainaru","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division, Oak Ridge National Laboratory 2 , Oak Ridge, Tennessee 37831,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0959-3431","authenticated-orcid":false,"given":"Roland","family":"B\u00f6hmer","sequence":"additional","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Physik, Technische Universit\u00e4t Dortmund 3 , Dortmund 44227,","place":["Germany"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7396-4407","authenticated-orcid":false,"given":"Shiwang","family":"Cheng","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering and Materials Science, Michigan State University 1 , East Lansing, Michigan 48824,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,10,1]]},"reference":[{"key":"2025100107340535700_c1","volume-title":"Theory of Simple Liquids","year":"1986"},{"issue":"11","key":"2025100107340535700_c2","doi-asserted-by":"publisher","first-page":"7113","DOI":"10.1063\/1.457656","article-title":"Rotational motion in molecular liquids","volume":"91","year":"1989","journal-title":"J.\u00a0Chem. Phys."},{"issue":"12","key":"2025100107340535700_c3","doi-asserted-by":"publisher","first-page":"124108","DOI":"10.1063\/1.5046511","article-title":"Statistical field theory for polar fluids","volume":"149","year":"2018","journal-title":"J.\u00a0Chem. Phys."},{"issue":"33","key":"2025100107340535700_c4","doi-asserted-by":"publisher","first-page":"R411","DOI":"10.1088\/0953-8984\/12\/33\/201","article-title":"The effect of dipolar forces on the structure and thermodynamics of classical fluids","volume":"12","year":"2000","journal-title":"J.\u00a0Phys.: Condens. Matter"},{"issue":"33","key":"2025100107340535700_c5","doi-asserted-by":"publisher","first-page":"9389","DOI":"10.1021\/acs.jpcb.1c03511","article-title":"Polymers with dynamic bonds: Adaptive functional materials for a sustainable future","volume":"125","year":"2021","journal-title":"J.\u00a0Phys. Chem. B"},{"issue":"16","key":"2025100107340535700_c6","doi-asserted-by":"publisher","first-page":"2961","DOI":"10.1039\/c8sm00044a","article-title":"Dynamics of associative polymers","volume":"14","year":"2018","journal-title":"Soft Matter"},{"issue":"31","key":"2025100107340535700_c7","doi-asserted-by":"publisher","first-page":"13200","DOI":"10.1021\/jp953538d","article-title":"Supercooled liquids and glasses","volume":"100","year":"1996","journal-title":"J.\u00a0Phys. Chem."},{"issue":"1","key":"2025100107340535700_c8","doi-asserted-by":"publisher","first-page":"010606","DOI":"10.1103\/physreve.102.010606","article-title":"Dipole-dipole correlations and the Debye process in the dielectric response of nonassociating glass forming liquids","volume":"102","year":"2020","journal-title":"Phys. Rev. E"},{"issue":"12","key":"2025100107340535700_c9","doi-asserted-by":"publisher","first-page":"120902","DOI":"10.1063\/5.0254534","article-title":"On the spectral shape of the structural relaxation in supercooled liquids","volume":"162","year":"2025","journal-title":"J.\u00a0Chem. Phys."},{"issue":"17","key":"2025100107340535700_c10","doi-asserted-by":"publisher","first-page":"174504","DOI":"10.1063\/5.0145433","article-title":"Non-simple flow behavior in a polar van der Waals liquid: Structural relaxation under scrutiny","volume":"158","year":"2023","journal-title":"J.\u00a0Chem. Phys."},{"issue":"27","key":"2025100107340535700_c11","doi-asserted-by":"publisher","first-page":"6191","DOI":"10.1021\/acs.jpcb.3c02335","article-title":"Nature of dielectric response of phenyl alcohols","volume":"127","year":"2023","journal-title":"J.\u00a0Phys. Chem. B"},{"issue":"10","key":"2025100107340535700_c12","doi-asserted-by":"publisher","first-page":"104510","DOI":"10.1063\/1.4867913","article-title":"Observation of the slow, Debye-like relaxation in hydrogen-bonded liquids by dynamic light scattering","volume":"140","year":"2014","journal-title":"J.\u00a0Chem. Phys."},{"issue":"13","key":"2025100107340535700_c13","doi-asserted-by":"publisher","first-page":"134505","DOI":"10.1063\/5.0168588","article-title":"The Debye\u2019s model for the dielectric relaxation of liquid water and the role of cross-dipolar correlations. A MD-simulations study","volume":"159","year":"2023","journal-title":"J.\u00a0Chem. Phys."},{"issue":"3","key":"2025100107340535700_c14","doi-asserted-by":"publisher","first-page":"034608","DOI":"10.1103\/physreve.109.034608","article-title":"Experimental examination of dipole-dipole cross-correlations by dielectric spectroscopy, depolarized dynamic light scattering, and computer simulations of molecular dynamics","volume":"109","year":"2024","journal-title":"Phys. Rev. E"},{"issue":"2","key":"2025100107340535700_c15","doi-asserted-by":"publisher","first-page":"025501","DOI":"10.1103\/physrevlett.129.025501","article-title":"Computational evidence for the crucial role of dipole cross-correlations in polar glass-forming liquids","volume":"129","year":"2022","journal-title":"Phys. Rev. Lett."},{"issue":"9","key":"2025100107340535700_c16","doi-asserted-by":"publisher","first-page":"5118","DOI":"10.3390\/ijms23095118","article-title":"NMR relaxometry accessing the relaxation spectrum in molecular glass formers","volume":"23","year":"2022","journal-title":"Int. J. Mol. Sci."},{"issue":"14","key":"2025100107340535700_c17","doi-asserted-by":"publisher","first-page":"3685","DOI":"10.1021\/acs.jpclett.1c00753","article-title":"Generic structural relaxation in supercooled liquids","volume":"12","year":"2021","journal-title":"J.\u00a0Phys. Chem. Lett."},{"issue":"5","key":"2025100107340535700_c18","doi-asserted-by":"publisher","first-page":"058201","DOI":"10.1103\/physrevlett.132.058201","article-title":"Hydrogen bonding exchange and supramolecular dynamics of monohydroxy alcohols","volume":"132","year":"2024","journal-title":"Phys. Rev. Lett."},{"issue":"9","key":"2025100107340535700_c19","doi-asserted-by":"publisher","first-page":"098201","DOI":"10.1103\/physrevlett.130.098201","article-title":"Molecular mechanism of the Debye relaxation in monohydroxy alcohols revealed from rheo-dielectric spectroscopy","volume":"130","year":"2023","journal-title":"Phys. Rev. Lett."},{"issue":"14","key":"2025100107340535700_c20","doi-asserted-by":"publisher","first-page":"144502","DOI":"10.1063\/1.4755754","article-title":"Experimental studies of Debye-like process and structural relaxation in mixtures of 2-ethyl-1-hexanol and 2-ethyl-1-hexyl bromide","volume":"137","year":"2012","journal-title":"J.\u00a0Chem. Phys."},{"issue":"23","key":"2025100107340535700_c21","doi-asserted-by":"publisher","first-page":"234501","DOI":"10.1063\/1.4986866","article-title":"Connecting structurally and dynamically detected signatures of supramolecular Debye liquids","volume":"147","year":"2017","journal-title":"J.\u00a0Chem. Phys."},{"key":"2025100107340535700_c22","doi-asserted-by":"publisher","first-page":"384","DOI":"10.1016\/j.jnoncrysol.2014.07.018","article-title":"Mixed Debye-type liquids studied by dielectric, shear mechanical, nuclear magnetic resonance, and near-infrared spectroscopy","volume":"407","year":"2015","journal-title":"J.\u00a0Non-Cryst. Solids"},{"issue":"4","key":"2025100107340535700_c23","doi-asserted-by":"publisher","first-page":"125","DOI":"10.1016\/j.physrep.2014.07.005","article-title":"Structure and dynamics of monohydroxy alcohols\u2014Milestones towards their microscopic understanding, 100 years after Debye","volume":"545","year":"2014","journal-title":"Phys. Rep."},{"issue":"25","key":"2025100107340535700_c24","doi-asserted-by":"publisher","first-page":"258303","DOI":"10.1103\/physrevlett.105.258303","article-title":"Nuclear-magnetic-resonance measurements reveal the origin of the Debye process in monohydroxy alcohols","volume":"105","year":"2010","journal-title":"Phys. Rev. Lett."},{"key":"2025100107340535700_c25","volume-title":"Dielectric Behavior and Structure: Dielectric Constant and Loss, Dipole Moment and Molecular Structure","year":"1955"},{"issue":"14","key":"2025100107340535700_c26","doi-asserted-by":"publisher","first-page":"144503","DOI":"10.1063\/1.4823998","article-title":"Dynamics of glass-forming liquids. XVII. Dielectric relaxation and intermolecular association in a series of isomeric octyl alcohols","volume":"139","year":"2013","journal-title":"J.\u00a0Chem. Phys."},{"key":"2025100107340535700_c27","volume-title":"Theory of Dielectrics : Dielectric Constant and Dielectric Loss","year":"1949"},{"issue":"10","key":"2025100107340535700_c28","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.\u00a0Chem. Phys."},{"issue":"3","key":"2025100107340535700_c29","doi-asserted-by":"publisher","first-page":"279","DOI":"10.1016\/s0010-4655(01)00217-x","article-title":"A generalized regularization method for nonlinear ill-posed problems enhanced for nonlinear regularization terms","volume":"139","year":"2001","journal-title":"Comput. Phys. Commun."},{"issue":"16","key":"2025100107340535700_c30","doi-asserted-by":"publisher","first-page":"6149","DOI":"10.1021\/acs.macromol.7b00825","article-title":"Analyzing the interfacial layer properties in polymer nanocomposites by broadband dielectric spectroscopy","volume":"50","year":"2017","journal-title":"Macromolecules"},{"issue":"19","key":"2025100107340535700_c31","doi-asserted-by":"publisher","first-page":"194704","DOI":"10.1063\/1.4935595","article-title":"Revealing spatially heterogeneous relaxation in a model nanocomposite","volume":"143","year":"2015","journal-title":"J.\u00a0Chem. Phys."},{"issue":"3","key":"2025100107340535700_c32","doi-asserted-by":"publisher","first-page":"038302","DOI":"10.1103\/physrevlett.116.038302","article-title":"Unexpected molecular weight effect in polymer nanocomposites","volume":"116","year":"2016","journal-title":"Phys. Rev. Lett."},{"issue":"1","key":"2025100107340535700_c33","doi-asserted-by":"publisher","first-page":"245","DOI":"10.1002\/zaac.19261560121","article-title":"Die Abh\u00e4ngigkeit der Viscosit\u00e4t von der Temperatur bie unterk\u00fchlten Fl\u00fcssigkeiten","volume":"156","year":"1926","journal-title":"Z. Anorg. Allg. Chem."},{"key":"2025100107340535700_c34","doi-asserted-by":"publisher","first-page":"339","DOI":"10.1111\/j.1151-2916.1925.tb16731.x","article-title":"Analysis of recent measurement of the viscosity of glasses","volume":"8","year":"1925","journal-title":"J.\u00a0Am. Ceram. Soc."},{"key":"2025100107340535700_c35","article-title":"Broadband dielectric spectroscopy and its application in polymeric materials","volume-title":"Macromolecular Engineering","year":"2022"},{"key":"2025100107340535700_c36","volume-title":"Broadband Dielectric Spectroscopy","year":"2002"},{"issue":"6","key":"2025100107340535700_c37","doi-asserted-by":"publisher","first-page":"064512","DOI":"10.1063\/1.3549123","article-title":"Diluting the hydrogen bonds in viscous solutions of n-butanol with n-bromobutane: II. A comparison of rotational and translational motions","volume":"134","year":"2011","journal-title":"J.\u00a0Chem. Phys."},{"issue":"1","key":"2025100107340535700_c38","doi-asserted-by":"publisher","first-page":"752","DOI":"10.1021\/acsnano.6b07172","article-title":"Big effect of small nanoparticles: A shift in paradigm for polymer nanocomposites","volume":"11","year":"2017","journal-title":"ACS Nano"},{"issue":"1","key":"2025100107340535700_c39","doi-asserted-by":"publisher","first-page":"302","DOI":"10.1021\/acs.macromol.9b01584","article-title":"Decoupling the polymer dynamics and the nanoparticle network dynamics of polymer nanocomposites through dielectric spectroscopy and rheology","volume":"53","year":"2020","journal-title":"Macromolecules"},{"issue":"4","key":"2025100107340535700_c40","doi-asserted-by":"publisher","first-page":"322","DOI":"10.1007\/s003970000137","article-title":"Van Gurp-Palmen-plot: A way to characterize polydispersity of linear polymers","volume":"40","year":"2001","journal-title":"Rheol. Acta"},{"key":"2025100107340535700_c41","volume-title":"Viscoelastic Properties of Polymers","year":"1980"},{"issue":"9","key":"2025100107340535700_c42","doi-asserted-by":"publisher","first-page":"098301","DOI":"10.1103\/physrevlett.112.098301","article-title":"Shear-modulus investigations of monohydroxy alcohols: Evidence for a short-chain-polymer rheological response","volume":"112","year":"2014","journal-title":"Phys. Rev. Lett."},{"issue":"2","key":"2025100107340535700_c43","doi-asserted-by":"publisher","first-page":"024304","DOI":"10.1103\/physrevb.99.024304","article-title":"Linear complex susceptibility of long-range interacting dipoles with thermal agitation and weak external ac fields","volume":"99","year":"2019","journal-title":"Phys. Rev. B"},{"key":"2025100107340535700_c44","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1007\/978-3-319-72706-6","article-title":"Scaling of suprastructure and dynamics in pure and mixed Debye liquids","volume-title":"The Scaling of Relaxation Processes","author":"Kremer","year":"2018"},{"issue":"5","key":"2025100107340535700_c45","doi-asserted-by":"publisher","first-page":"466","DOI":"10.1002\/jps.2600820507","article-title":"Molecular organization of liquid n-Octanol: An X-ray diffraction analysis","volume":"82","year":"1993","journal-title":"J.\u00a0Pharm. Sci."},{"issue":"4","key":"2025100107340535700_c46","doi-asserted-by":"publisher","first-page":"2672","DOI":"10.1021\/acs.jpcc.9b09803","article-title":"Relationship between nanoscale supramolecular structure, effectiveness of hydrogen bonds, and appearance of Debye process","volume":"124","year":"2020","journal-title":"J.\u00a0Phys. Chem. C"},{"issue":"37","key":"2025100107340535700_c47","doi-asserted-by":"publisher","first-page":"10848","DOI":"10.1021\/jp058279z","article-title":"Relationship between the charge distribution and dipole moment functions of CO and the related molecules CS, SiO, and SiS","volume":"110","year":"2006","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"16","key":"2025100107340535700_c48","doi-asserted-by":"publisher","first-page":"167802","DOI":"10.1103\/physrevlett.109.167802","article-title":"Watching hydrogen-bonded structures in an alcohol convert from rings to chains","volume":"109","year":"2012","journal-title":"Phys. Rev. Lett."},{"issue":"10","key":"2025100107340535700_c49","doi-asserted-by":"publisher","first-page":"101104","DOI":"10.1063\/1.4895095","article-title":"Communication: Supramolecular structures in monohydroxy alcohols: Insights from shear-mechanical studies of a systematic series of octanol structural isomers","volume":"141","year":"2014","journal-title":"J.\u00a0Chem. Phys."},{"issue":"05","key":"2025100107340535700_c50","doi-asserted-by":"publisher","first-page":"054501","DOI":"10.1063\/5.0160894","article-title":"Revealing complex relaxation behavior of monohydroxy alcohols in a series of octanol isomers","volume":"159","year":"2023","journal-title":"J.\u00a0Chem. Phys."},{"issue":"14","key":"2025100107340535700_c51","doi-asserted-by":"publisher","first-page":"5792","DOI":"10.1021\/acs.jpclett.0c01499","article-title":"Entropic nature of the Debye relaxation in glass-forming monoalcohols","volume":"11","year":"2020","journal-title":"J.\u00a0Phys. Chem. Lett."},{"issue":"9","key":"2025100107340535700_c52","doi-asserted-by":"publisher","first-page":"094505","DOI":"10.1063\/1.4793469","article-title":"Debye relaxation and 250\u00a0K anomaly in glass forming monohydroxy alcohols","volume":"138","year":"2013","journal-title":"J.\u00a0Chem. Phys."},{"issue":"6291","key":"2025100107340535700_c53","doi-asserted-by":"publisher","first-page":"1308","DOI":"10.1126\/science.aaf3182","article-title":"Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers","volume":"352","year":"2016","journal-title":"Science"},{"issue":"9","key":"2025100107340535700_c54","doi-asserted-by":"publisher","first-page":"094904","DOI":"10.1063\/1.5143360","article-title":"Correlation between the temperature evolution of the interfacial region and the growing dynamic cooperativity length scale","volume":"152","year":"2020","journal-title":"J.\u00a0Chem. Phys."},{"issue":"22","key":"2025100107340535700_c55","doi-asserted-by":"publisher","first-page":"225702","DOI":"10.1103\/physrevlett.111.225702","article-title":"Cooperativity and the freezing of molecular motion at the glass transition","volume":"111","year":"2013","journal-title":"Phys. Rev. Lett."},{"issue":"11","key":"2025100107340535700_c56","doi-asserted-by":"publisher","first-page":"2960","DOI":"10.1021\/acs.jpcb.0c10970","article-title":"Is a dissociation process underlying the molecular origin of the Debye process in monohydroxy alcohols?","volume":"125","year":"2021","journal-title":"J.\u00a0Phys. Chem. B"},{"key":"2025100107340535700_c57","volume-title":"Electrical Properties of Polymers","year":"2004"},{"key":"2025100107340535700_c58","doi-asserted-by":"publisher","first-page":"127045","DOI":"10.1016\/j.molliq.2025.127045","article-title":"Effect of high pressure on the molecular dynamics of halogen monoalcohols","volume":"423","year":"2025","journal-title":"J.\u00a0Mol. Liq."},{"issue":"42","key":"2025100107340535700_c59","doi-asserted-by":"publisher","first-page":"9102","DOI":"10.1021\/acs.jpcb.3c02092","article-title":"Experimental and computational approach to studying supramolecular structures in propanol and its halogen derivatives","volume":"127","year":"2023","journal-title":"J.\u00a0Phys. Chem. B"},{"issue":"2","key":"2025100107340535700_c60","doi-asserted-by":"publisher","first-page":"025702","DOI":"10.1103\/physrevlett.116.025702","article-title":"Universal behavior of dielectric responses of glass formers: Role of dipole-dipole interactions","volume":"116","year":"2016","journal-title":"Phys. Rev. Lett."},{"issue":"6829","key":"2025100107340535700_c61","doi-asserted-by":"publisher","first-page":"663","DOI":"10.1038\/35070517","article-title":"A thermodynamic connection to the fragility of glass-forming liquids","volume":"410","year":"2001","journal-title":"Nature"}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0284312\/20721582\/134501_1_5.0284312.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0284312\/20721582\/134501_1_5.0284312.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,1]],"date-time":"2025-10-01T11:34:16Z","timestamp":1759318456000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/163\/13\/134501\/3365386\/Evidence-for-supramolecular-dynamics-of-non"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,1]]},"references-count":61,"journal-issue":{"issue":"13","published-print":{"date-parts":[[2025,10,7]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0284312","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[2025,10,7]]},"published":{"date-parts":[[2025,10,1]]},"article-number":"134501"}}