{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,7]],"date-time":"2026-08-07T15:39:57Z","timestamp":1786117197842,"version":"build-2736575974"},"reference-count":42,"publisher":"American Chemical Society (ACS)","issue":"31","license":[{"start":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T00:00:00Z","timestamp":1785110400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006094","name":"University of Delaware","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100006094","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100012878","name":"Department of Physics and Astronomy, University of Delaware","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100012878","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R21AG085412"],"award-info":[{"award-number":["R21AG085412"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Polarization-resolved infrared pump-stimulated Raman probe spectroscopy was used to measure the lifetimes of OH stretching vibrations in liquid water, giving rise to polarized and depolarized Raman signals. The lifetime of the OH stretch for the polarized Raman was determined to be 200 fs, in excellent agreement with previous measurements. The lifetime of OH stretches contributing to the depolarized Raman signal was determined here for the first time and was found to be at least two times longer (\u2265400 fs). With the support of mixed quantum-classical line shape calculations, the experimental lifetimes were rationalized in terms of the extent of the coupling between the OH stretching modes as well as their coupling to the overtone of water bending vibrations. OH stretches that participate in an extensive network of coupled vibrations contribute to the polarized Raman spectrum, while mainly uncoupled OH modes give rise to the depolarized Raman signals.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c00970","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:09:42Z","timestamp":1785848982000},"page":"8790-8797","source":"Crossref","is-referenced-by-count":0,"title":["The Origin of\nthe Frequency-Dependence of OH Stretch\nVibrational Lifetimes in Liquid Water"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9159-4363","authenticated-orcid":true,"given":"Marcin","family":"Pastorczak","sequence":"first","affiliation":[{"name":"Polish Academy of Sciences , , Kasprzaka 44\/52 , ,","place":["Warsaw, Poland, 01-224"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Czes\u0142aw","family":"Radzewicz","sequence":"additional","affiliation":[{"name":"Polish Academy of Sciences , , Kasprzaka 44\/52 , ,","place":["Warsaw, Poland, 01-224"]},{"name":"University of Warsaw , , Pasteura 5 , ,","place":["Warsaw, Poland, 02-093"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1021-5550","authenticated-orcid":true,"given":"Aritri","family":"Biswas","sequence":"additional","affiliation":[{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9422-7203","authenticated-orcid":true,"given":"Alexei A.","family":"Kananenka","sequence":"additional","affiliation":[{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,27]]},"reference":[{"issue":"43","key":"2026080609083674100_cit1","doi-asserted-by":"publisher","first-page":"15324","DOI":"10.1002\/anie.201908876","article-title":"Modification of Enzyme Activity by\nVibrational Strong Coupling of Water","volume":"58","author":"Vergauwe","year":"2019","journal-title":"Angew.\nChem., Int. Ed."},{"issue":"5493","key":"2026080609083674100_cit2","doi-asserted-by":"publisher","first-page":"950","DOI":"10.1126\/science.290.5493.950","article-title":"Stretched\nWater Is More Reactive","volume":"290","author":"Schatz","year":"2000","journal-title":"Science"},{"issue":"4","key":"2026080609083674100_cit3","doi-asserted-by":"publisher","first-page":"1352","DOI":"10.1039\/D0SC05431C","article-title":"Universal quenching of common fluorescent probes by\nwater and alcohols","volume":"12","author":"Maillard","year":"2021","journal-title":"Chemical Science"},{"issue":"12","key":"2026080609083674100_cit4","doi-asserted-by":"publisher","first-page":"5340","DOI":"10.1021\/acs.biomac.2c01156","article-title":"In Situ Identification\nof Secondary Structures in Unpurified Bombyx mori Silk Fibrils Using\nPolarized Two-Dimensional Infrared Spectroscopy","volume":"23","author":"Giubertoni","year":"2022","journal-title":"Biomacromolecules"},{"issue":"22","key":"2026080609083674100_cit5","doi-asserted-by":"publisher","first-page":"10433","DOI":"10.1039\/C4CP00671B","article-title":"Conformation of\nthe neurotransmitter \u03b3-aminobutyric acid in liquid water","volume":"16","author":"Ottosson","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"30","key":"2026080609083674100_cit6","doi-asserted-by":"publisher","first-page":"9466","DOI":"10.1021\/jacs.8b03547","article-title":"Water Dynamics in\nPolyacrylamide Hydrogels","volume":"140","author":"Yan","year":"2018","journal-title":"J. Am. Chem. Soc."},{"issue":"30","key":"2026080609083674100_cit7","doi-asserted-by":"publisher","first-page":"9634","DOI":"10.1021\/jacs.6b05122","article-title":"Interplay\nof Ion-Water and Water-Water Interactions within the Hydration Shells\nof Nitrate and Carbonate Directly Probed with 2D IR Spectroscopy","volume":"138","author":"Fournier","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026080609083674100_cit8","doi-asserted-by":"publisher","first-page":"060901","DOI":"10.1063\/5.0182665","article-title":"The structure\nof water: A historical perspective","volume":"160","author":"Finney","year":"2024","journal-title":"J. Chem.\nPhys."},{"issue":"5","key":"2026080609083674100_cit9","doi-asserted-by":"publisher","first-page":"594","DOI":"10.1016\/S0009-2614(03)00314-2","article-title":"Vibrational\nrelaxation and spectral\nevolution following ultrafast OH stretch excitation of water","volume":"371","author":"Pakoulev","year":"2003","journal-title":"Chem. Phys. Lett."},{"issue":"42","key":"2026080609083674100_cit10","doi-asserted-by":"publisher","first-page":"9054","DOI":"10.1021\/jp048545t","article-title":"Vibrational Substructure\nin the OH Stretching Transition of Water and HOD","volume":"108","author":"Wang","year":"2004","journal-title":"J. Phys. Chem. A"},{"issue":"3","key":"2026080609083674100_cit11","doi-asserted-by":"publisher","first-page":"329","DOI":"10.1016\/j.cplett.2003.12.079","article-title":"Comment on\n\u2018Vibrational relaxation\nand spectral evolution following ultrafast OH stretch excitation of\nwater\u2019 by A. Pakoulev, Z. Wang, D.D. Dlott","volume":"385","author":"Bakker","year":"2004","journal-title":"Chem. Phys. Lett."},{"issue":"4","key":"2026080609083674100_cit12","doi-asserted-by":"publisher","first-page":"1708","DOI":"10.1063\/1.1485966","article-title":"Temperature dependence\nof vibrational relaxation in\nliquid H2O","volume":"117","author":"Lock","year":"2002","journal-title":"J. Chem. Phys."},{"issue":"4","key":"2026080609083674100_cit13","doi-asserted-by":"publisher","first-page":"329","DOI":"10.1016\/j.cplett.2006.01.081","article-title":"Vibrational\nrelaxation of pure liquid water","volume":"421","author":"Lindner","year":"2006","journal-title":"Chem. Phys.\nLett."},{"key":"2026080609083674100_cit14","doi-asserted-by":"publisher","first-page":"935","DOI":"10.1038\/nchem.1757","article-title":"Water vibrations\nhave strongly mixed intra- and intermolecular character","volume":"5","author":"Ramasesha","year":"2013","journal-title":"Nat. Chem."},{"issue":"7030","key":"2026080609083674100_cit15","doi-asserted-by":"publisher","first-page":"199","DOI":"10.1038\/nature03383","article-title":"Ultrafast memory\nloss and energy redistribution in the hydrogen bond network of liquid\nH2O","volume":"434","author":"Cowan","year":"2005","journal-title":"Nature"},{"issue":"2","key":"2026080609083674100_cit16","doi-asserted-by":"publisher","first-page":"437","DOI":"10.1073\/pnas.0705792105","article-title":"Temperature dependence of the two-dimensional\ninfrared spectrum of liquid H2O","volume":"105","author":"Kraemer","year":"2008","journal-title":"Proc. Natl. Acad. Sci. U. S. A."},{"key":"2026080609083674100_cit17","doi-asserted-by":"publisher","first-page":"8384","DOI":"10.1038\/ncomms9384","article-title":"Strong frequency dependence\nof vibrational relaxation in bulk and surface water reveals sub-picosecond\nstructural heterogeneity","volume":"6","author":"van der Post","year":"2015","journal-title":"Nat. Commun."},{"issue":"1","key":"2026080609083674100_cit18","doi-asserted-by":"publisher","first-page":"1258","DOI":"10.1038\/s41467-024-45388-8","article-title":"Unified picture of\nvibrational relaxation of OH stretch at the air\/water interface","volume":"15","author":"Sung","year":"2024","journal-title":"Nat. Commun."},{"issue":"9","key":"2026080609083674100_cit19","doi-asserted-by":"publisher","first-page":"094501","DOI":"10.1063\/1.4961752","article-title":"Anharmonic exciton dynamics and energy\ndissipation in liquid water from two-dimensional infrared spectroscopy","volume":"145","author":"De Marco","year":"2016","journal-title":"J. Chem. Phys."},{"issue":"31","key":"2026080609083674100_cit20","doi-asserted-by":"publisher","first-page":"16895","DOI":"10.1039\/C9CP00855A","article-title":"Femtosecond\ninfrared pump-stimulated\nRaman probe spectroscopy: the first application of the method to studies\nof vibrational relaxation pathways in the liquid HDO\/D2O system","volume":"21","author":"Pastorczak","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026080609083674100_cit21","doi-asserted-by":"publisher","first-page":"09026","DOI":"10.1051\/epjconf\/201920509026","article-title":"Femtosecond\ninfrared pump - stimulated Raman probe spectroscopy: the method and\nits first application to study vibrational relaxation pathway in liquid\nwater","volume":"205","author":"Pastorczak","year":"2019","journal-title":"EPJ. Web Conf."},{"issue":"22","key":"2026080609083674100_cit22","doi-asserted-by":"publisher","first-page":"224511","DOI":"10.1063\/1.2925258","article-title":"IR and Raman spectra of liquid water:\nTheory and interpretation","volume":"128","author":"Auer","year":"2008","journal-title":"J. Chem. Phys."},{"issue":"3","key":"2026080609083674100_cit23","doi-asserted-by":"publisher","first-page":"1498","DOI":"10.1021\/cr9001879","article-title":"Vibrational Spectroscopy\nas a Probe of Structure and\nDynamics in Liquid Water","volume":"110","author":"Bakker","year":"2010","journal-title":"Chem. Rev."},{"issue":"18","key":"2026080609083674100_cit24","doi-asserted-by":"publisher","first-page":"184505","DOI":"10.1063\/1.2188942","article-title":"Contribution\nof the asymmetric stretch, \u03bd3B1, to the\nfundamental Raman spectrum of water","volume":"124","author":"Walrafen","year":"2006","journal-title":"J. Chem.\nPhys."},{"issue":"8","key":"2026080609083674100_cit25","doi-asserted-by":"publisher","first-page":"1147","DOI":"10.1021\/j100652a010","article-title":"Raman spectra\nand an assignment of the vibrational\nstretching region of water","volume":"76","author":"Murphy","year":"1972","journal-title":"J. Phys. Chem."},{"issue":"24","key":"2026080609083674100_cit26","doi-asserted-by":"publisher","first-page":"244107","DOI":"10.1063\/1.5037113","article-title":"Fermi resonance in OH-stretch vibrational spectroscopy\nof liquid water and the water hexamer","volume":"148","author":"Kananenka","year":"2018","journal-title":"J. Chem.\nPhys."},{"issue":"10","key":"2026080609083674100_cit27","doi-asserted-by":"publisher","first-page":"1773","DOI":"10.1002\/jrs.6322","article-title":"Raman spectroscopy\nof isotopically\npure and diluted high- and low-density amorphous ices","volume":"53","author":"Ishihara","year":"2022","journal-title":"J. Raman Spectrosc."},{"issue":"10","key":"2026080609083674100_cit28","doi-asserted-by":"publisher","first-page":"1769","DOI":"10.1021\/acs.jpclett.6b00668","article-title":"Differences in the Vibrational Dynamics\nof H2O and D2O: Observation of Symmetric and\nAntisymmetric Stretching Vibrations in Heavy Water","volume":"7","author":"De Marco","year":"2016","journal-title":"J. Phys. Chem. Lett."},{"issue":"5","key":"2026080609083674100_cit29","doi-asserted-by":"publisher","first-page":"470","DOI":"10.1103\/PhysRev.55.470","article-title":"A New Infra-red\nAbsorption Band of Liquid Water at 2.52\u03bc","volume":"55","author":"Collins","year":"1939","journal-title":"Phys. Rev."},{"issue":"21","key":"2026080609083674100_cit30","doi-asserted-by":"publisher","first-page":"4843","DOI":"10.1021\/acs.jpcb.3c01334","article-title":"Combinational Vibration Modes in\nH2O\/HDO\/D2O Mixtures Detected Thanks to the\nSuperior Sensitivity of Femtosecond Stimulated Raman Scattering","volume":"127","author":"Pastorczak","year":"2023","journal-title":"J. Phys. Chem. B"},{"issue":"8","key":"2026080609083674100_cit31","doi-asserted-by":"publisher","first-page":"1238","DOI":"10.1021\/jp003158e","article-title":"Ultrafast Energy Equilibration in\nHydrogen-Bonded Liquids","volume":"105","author":"Lock","year":"2001","journal-title":"J. Phys. Chem. A"},{"issue":"4","key":"2026080609083674100_cit32","doi-asserted-by":"publisher","first-page":"1494","DOI":"10.1063\/1.479408","article-title":"Mechanism for vibrational\nrelaxation in water investigated by femtosecond infrared spectroscopy","volume":"111","author":"Nienhuys","year":"1999","journal-title":"J. Chem. Phys."},{"issue":"18","key":"2026080609083674100_cit33","doi-asserted-by":"publisher","first-page":"1162","DOI":"10.1103\/PhysRevLett.28.1162","article-title":"Direct Measurement of the Vibrational\nLifetimes of Molecules in Liquids","volume":"28","author":"Laubereau","year":"1972","journal-title":"Phys. Rev.\nLett."},{"issue":"8","key":"2026080609083674100_cit34","doi-asserted-by":"publisher","first-page":"084503","DOI":"10.1063\/1.4987153","article-title":"Delocalization\nand stretch-bend mixing of the HOH bend in liquid water","volume":"147","author":"Carpenter","year":"2017","journal-title":"J. Chem. Phys."},{"issue":"4","key":"2026080609083674100_cit35","doi-asserted-by":"publisher","first-page":"982","DOI":"10.1039\/B918314K","article-title":"Signatures of coherent\nvibrational energy transfer\nin IR and Raman line shapes for liquid water","volume":"12","author":"Yang","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"10","key":"2026080609083674100_cit36","doi-asserted-by":"publisher","first-page":"104105","DOI":"10.1063\/1.2766943","article-title":"Dynamical effects\nin line shapes for coupled chromophores:\nTime-averaging approximation","volume":"127","author":"Auer","year":"2007","journal-title":"J. Chem. Phys."},{"issue":"47","key":"2026080609083674100_cit37","doi-asserted-by":"publisher","first-page":"10754","DOI":"10.1021\/acs.jpcb.8b09910","article-title":"Disentangling Coupling Effects in\nthe Infrared Spectra of Liquid Water","volume":"122","author":"Hunter","year":"2018","journal-title":"J. Phys.\nChem. B"},{"issue":"24","key":"2026080609083674100_cit38","doi-asserted-by":"publisher","first-page":"5139","DOI":"10.1021\/acs.jpcb.9b02686","article-title":"OH-Stretch Raman\nMultivariate Curve\nResolution Spectroscopy of HOD\/H2O Mixtures","volume":"123","author":"Kananenka","year":"2019","journal-title":"J. Phys. Chem. B"},{"issue":"13","key":"2026080609083674100_cit39","doi-asserted-by":"publisher","first-page":"10120","DOI":"10.1039\/D3CP06255D","article-title":"The\nstrength of the OH-bend\/OH-stretch Fermi resonance in small water\nclusters","volume":"26","author":"Lu\u0308ttschwager","year":"2024","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"3","key":"2026080609083674100_cit40","doi-asserted-by":"publisher","first-page":"93","DOI":"10.1016\/0370-1573(74)90029-5","article-title":"Electrons\nin disordered systems and the theory of localization","volume":"13","author":"Thouless","year":"1974","journal-title":"Phys. Rep."},{"issue":"3","key":"2026080609083674100_cit41","doi-asserted-by":"publisher","first-page":"2136","DOI":"10.1364\/OE.20.002136","article-title":"Efficient spectral shift and compression\nof femtosecond\npulses by parametric amplification of chirped light","volume":"20","author":"Nejbauer","year":"2012","journal-title":"Opt. Express"},{"key":"2026080609083674100_cit42","doi-asserted-by":"publisher","first-page":"104953","DOI":"10.1016\/j.infrared.2023.104953","article-title":"Broadly tunable\nfemtosecond OPA pumped by 1030 nm Yb: KGW laser with a range of non-linear\ncrystals tested","volume":"135","author":"Nejbauer","year":"2023","journal-title":"Infrared Physics & Technology"}],"container-title":["The Journal of Physical\nChemistry Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpclett.6c00970","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/31\/8790\/66286534\/acs.jpclett.6c00970.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/31\/8790\/66286534\/acs.jpclett.6c00970.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T13:23:20Z","timestamp":1786022600000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article\/17\/31\/8790\/5234337\/The-Origin-of-the-Frequency-Dependence-of-OH"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,27]]},"references-count":42,"journal-issue":{"issue":"31","published-online":{"date-parts":[[2026,7,27]]},"published-print":{"date-parts":[[2026,8,6]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpclett.6c00970","relation":{},"ISSN":["1948-7185"],"issn-type":[{"value":"1948-7185","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,27]]}}}