{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T14:05:47Z","timestamp":1790863547767,"version":"4.1.0"},"reference-count":40,"publisher":"American Chemical Society (ACS)","issue":"39","license":[{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100016697","name":"Youth Innovation Technology Project of Higher School in Shandong Province","doi-asserted-by":"publisher","award":["2025KJG058"],"award-info":[{"award-number":["2025KJG058"]}],"id":[{"id":"10.13039\/100016697","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,1]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The linear-response polarizable continuum model (LR-PCM) is routinely used to optimize excited-state geometries in ESIPT systems, followed by single-point energy corrections with the state-specific PCM (SS-PCM). This mixed protocol implicitly assumes that the LR-PCM minimum coincides with the minimum on the SS-PCM potential energy surface (PES)\u2500an assumption that has never been systematically scrutinized in ESIPT systems. Here, we investigate this question using two flavonoid anions (API-B4 and LUT-B4-\u03b1\/\u03b2) with zero, one, or two explicit water molecules hydrogen-bonded to the C4\u2032\u2013O\u2013 group. By constructing one-dimensional potential energy curves along the O5\u2013H proton-transfer coordinate, we compare LR-PCM and SS-PCM descriptions. The ESIPT barrier is found to be nearly identical between the two models (differences &amp;lt; 0.5 kcal\/mol) and largely insensitive to explicit waters. Each explicit water molecule raises the S1 excitation energies by about 0.1 eV by stabilizing the HOMO more than the LUMO. More importantly, the keto minimum obtained with LR-PCM is not always a minimum on the SS-PCM PES. This discrepancy is correlated with the substantial increase in the excited-state dipole moment induced by SS-PCM and is consistently reproduced across three hybrid functionals (\u03c9B97X-D, CAM-B3LYP, M062X). Overall, this work provides new insight into the role of the SS-PCM-enhanced excited-state dipole moment in emission energy calculations.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c04063","type":"journal-article","created":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T16:02:25Z","timestamp":1789574545000},"page":"10291-10297","source":"Crossref","is-referenced-by-count":0,"title":["Linear-Response\nand State-Specific Polarizable Continuum\nModels Yield Different ESIPT Tautomer Geometries of Flavonoid Anions"],"prefix":"10.1021","volume":"130","author":[{"given":"Qin","family":"Yu","sequence":"first","affiliation":[{"name":"Yangtze University , , ,","place":["Jingzhou, China, 434023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiya","family":"Peng","sequence":"additional","affiliation":[{"name":"Yangtze University , , ,","place":["Jingzhou, China, 434023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Binghan","family":"Li","sequence":"additional","affiliation":[{"name":"Yangtze University , , ,","place":["Jingzhou, China, 434023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fengling","family":"Mei","sequence":"additional","affiliation":[{"name":"Yangtze University , , ,","place":["Jingzhou, China, 434023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3928-793X","authenticated-orcid":true,"given":"Jian","family":"Luo","sequence":"additional","affiliation":[{"name":"Yangtze University , , ,","place":["Jingzhou, China, 434023"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,16]]},"reference":[{"key":"2026100109061404200_cit1","doi-asserted-by":"publisher","first-page":"1681","DOI":"10.1021\/acs.accounts.8b00172","article-title":"Unraveling the Detailed Mechanism of Excited-State Proton Transfer","volume":"51","author":"Zhou","year":"2018","journal-title":"Acc. Chem. Res."},{"issue":"5","key":"2026100109061404200_cit2","doi-asserted-by":"publisher","DOI":"10.1002\/agt2.160","article-title":"ESIPT-based AIE luminogens: Design\nstrategies, applications, and\nmechanisms","volume":"3","author":"Zhou","year":"2022","journal-title":"Aggregate"},{"key":"2026100109061404200_cit3","doi-asserted-by":"publisher","first-page":"111994","DOI":"10.1016\/j.dyepig.2024.111994","article-title":"Advancements in ESIPT probe research\nover the past three years based on different fluorophores","volume":"224","author":"Lu","year":"2024","journal-title":"Dyes Pigm."},{"key":"2026100109061404200_cit4","doi-asserted-by":"publisher","first-page":"4190","DOI":"10.1364\/OL.532228","article-title":"Theoretical\nstudy of the substituent effects on the ESIPT mechanism\nof salicylideneaniline and the TICT photochemistry reactions","volume":"49","author":"Yin","year":"2024","journal-title":"Opt. Lett."},{"key":"2026100109061404200_cit5","doi-asserted-by":"publisher","first-page":"7112","DOI":"10.1021\/acs.langmuir.5c05421","article-title":"Unlocking Photocyclization via Hydrogen-Bond Disruption: A Theoretical\nInvestigation of Esterification-Gated Diarylethene Switches","volume":"42","author":"Zhang","year":"2026","journal-title":"Langmuir"},{"key":"2026100109061404200_cit6","doi-asserted-by":"publisher","first-page":"4708","DOI":"10.1063\/1.1394921","article-title":"Time-dependent density functional\ntheory for molecules\nin liquid solutions","volume":"115","author":"Cossi","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2026100109061404200_cit7","doi-asserted-by":"publisher","first-page":"2999","DOI":"10.1021\/cr9904009","article-title":"Quantum mechanical\ncontinuum solvation\nmodels","volume":"105","author":"Tomasi","year":"2005","journal-title":"Chem. Rev."},{"key":"2026100109061404200_cit8","doi-asserted-by":"publisher","first-page":"125607","DOI":"10.1016\/j.saa.2024.125607","article-title":"A TDDFT exploration\non the excited-state intramolecular proton transfer in 2-(2\u2032-hydroxyphenyl)-benzimidazole\nderivatives","volume":"329","author":"Hu","year":"2025","journal-title":"Spectrochim. Acta, Part A"},{"key":"2026100109061404200_cit9","doi-asserted-by":"publisher","first-page":"5725","DOI":"10.1021\/acs.jpcb.6c01181","article-title":"Excited-State Intramolecular\nProton\nTransfer of Deprotonated Fisetin in Poly(vinyl alcohol) Films","volume":"130","author":"Tan","year":"2026","journal-title":"J. Phys. Chem. B"},{"key":"2026100109061404200_cit10","doi-asserted-by":"publisher","first-page":"113087","DOI":"10.1016\/j.jphotobiol.2024.113087","article-title":"Excited-state\nantioxidant activity for apigenin based on external electric field-modulated\nESIPT behavior: TD-DFT and molecular docking calculations","volume":"262","author":"Tang","year":"2025","journal-title":"J. Photochem. Photobiol., B"},{"key":"2026100109061404200_cit11","doi-asserted-by":"publisher","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development\nof the colle-salvetti\ncorrelation-energy formula into a functional of the electron-density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"2026100109061404200_cit12","doi-asserted-by":"publisher","first-page":"336","DOI":"10.1016\/j.jphotochem.2018.11.018","article-title":"Performance of Time-Dependent Density Functional Theory on Twisted\nIntramolecular Charge Transfer State of Emerging Visible Light Photoswitches","volume":"371","author":"Liu","year":"2019","journal-title":"J. Photochem. Photobiol., A"},{"key":"2026100109061404200_cit13","doi-asserted-by":"publisher","first-page":"2307","DOI":"10.1039\/C8CP06969G","article-title":"First-principles investigation of\nthe double ESIPT process in a thiophene-based dye","volume":"21","author":"Ve\u0301rite\u0301","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"15","key":"2026100109061404200_cit14","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2024.2442752","article-title":"Theoretical investigation on excited state intramolecular\nproton transfer of 5-hydroxy-6,7,4\u2019-trimethoxyflavone: state\nspecific solvation approach versus linear response solvation","volume":"123","author":"Das","year":"2025","journal-title":"Mol. Phys."},{"issue":"7","key":"2026100109061404200_cit15","doi-asserted-by":"publisher","first-page":"074504","DOI":"10.1063\/1.2757168","article-title":"Toward effective\nand\nreliable fluorescence energies in solution by a new state specific\npolarizable continuum model time dependent density functional theory\napproach","volume":"127","author":"Improta","year":"2007","journal-title":"J. Chem. Phys."},{"key":"2026100109061404200_cit16","doi-asserted-by":"publisher","first-page":"5782","DOI":"10.1021\/acs.jctc.5b00679","article-title":"Electronic Excitations\nin Solution: The Interplay between State Specific Approaches and a\nTime-Dependent Density Functional Theory Description","volume":"11","author":"Guido","year":"2015","journal-title":"J. Chem. Theory Comput."},{"key":"2026100109061404200_cit17","doi-asserted-by":"publisher","first-page":"3127","DOI":"10.1021\/ct400392r","article-title":"Boranil and\nRelated NBO Dyes: Insights From Theory","volume":"9","author":"Chibani","year":"2013","journal-title":"J. Chem.\nTheory Comput."},{"key":"2026100109061404200_cit18","doi-asserted-by":"publisher","first-page":"3925","DOI":"10.1021\/ct500328t","article-title":"Excited State\nGeometries and Vertical Emission Energies of Solvated Dyes for DSSC:\nA PCM\/TD-DFT Benchmark Study","volume":"10","author":"Bernini","year":"2014","journal-title":"J. Chem. Theory\nComput."},{"issue":"5","key":"2026100109061404200_cit19","doi-asserted-by":"publisher","first-page":"054103","DOI":"10.1063\/1.2222364","article-title":"A state-specific\npolarizable continuum model time dependent density functional theory\nmethod for excited state calculations in solution","volume":"125","author":"Improta","year":"2006","journal-title":"J. Chem. Phys."},{"key":"2026100109061404200_cit20","doi-asserted-by":"publisher","first-page":"116817","DOI":"10.1016\/j.jphotochem.2025.116817","article-title":"Excited state intramolecular\nproton transfer reaction in 4\u2032,5-dimethoxy-3-hydroxyflavone:\npartial shielding of intermolecular H-bonding with protic molecules\nby 5-OCH3 group and its impact on ESIPT rate and fluorescence spectra","volume":"472","author":"Doroshenko","year":"2026","journal-title":"J. Photochem. Photobiol., A"},{"key":"2026100109061404200_cit21","doi-asserted-by":"publisher","first-page":"121991","DOI":"10.1016\/j.saa.2022.121991","article-title":"Uncovering\nthe dependence of ESIPT\nbehaviors and fluorescence properties of two new benzothiazole-based\nfluorophores on solvent polarity: A TD-DFT study","volume":"286","author":"Liang","year":"2023","journal-title":"Spectrochim. Acta, Part A"},{"key":"2026100109061404200_cit22","doi-asserted-by":"publisher","first-page":"140189","DOI":"10.1016\/j.cplett.2022.140189","article-title":"Ultrafast excited state dynamics\nof two non-emissive flavonoids that undergo excited state intramolecular\nproton transfer in solution","volume":"811","author":"Han","year":"2023","journal-title":"Chem. Phys. Lett."},{"key":"2026100109061404200_cit23","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.jphotochemrev.2014.09.005","article-title":"Thermodynamic vs.\nkinetic control\nof excited-state proton transfer reactions","volume":"22","author":"Tomin","year":"2015","journal-title":"J. Photochem. Photobiol., C"},{"key":"2026100109061404200_cit24","doi-asserted-by":"publisher","first-page":"46","DOI":"10.1016\/j.jlumin.2018.10.024","article-title":"Different\ntypes of hydrogen-bonded\ncomplexes would accelerate or delay the excited state proton transfer\nin 3-hydroxyflavone","volume":"206","author":"Yang","year":"2019","journal-title":"J. Lumin."},{"key":"2026100109061404200_cit25","doi-asserted-by":"publisher","first-page":"112039","DOI":"10.1016\/j.colsurfb.2021.112039","article-title":"New insights\ninto ESIPT mechanism of three sunscreen compounds in solution: A combined\nexperimental and theoretical study","volume":"207","author":"Ji","year":"2021","journal-title":"Colloid.\nSurf. B"},{"key":"2026100109061404200_cit26","doi-asserted-by":"publisher","first-page":"89","DOI":"10.1016\/S0009-2614(01)00399-2","article-title":"Spectroscopy and\nDynamics of Excited-State Intramolecular Proton-Transfer Reaction\nin 5-Hydroxyflavone","volume":"340","author":"Chou","year":"2001","journal-title":"Chem. Phys. Lett."},{"key":"2026100109061404200_cit27","doi-asserted-by":"publisher","first-page":"12572","DOI":"10.1039\/c3cp44267e","article-title":"Fluorescence\nBehavior of (Selected) Flavonols: A Combined Experimental and Computational\nStudy","volume":"15","author":"Hofener","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026100109061404200_cit28","doi-asserted-by":"publisher","first-page":"26870","DOI":"10.1039\/C7CP03845C","article-title":"Quercetin\nand Its Analogues: Optical and Acido-Basic Properties","volume":"19","author":"Biler","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026100109061404200_cit29","doi-asserted-by":"publisher","first-page":"124096","DOI":"10.1016\/j.talanta.2022.124096","article-title":"Acidity constants\nof hydroxyl groups placed in several flavonoids: Two flavanones, two\nflavones and five flavonols","volume":"253","author":"Fuguet","year":"2023","journal-title":"Talanta"},{"key":"2026100109061404200_cit30","doi-asserted-by":"publisher","first-page":"126146","DOI":"10.1016\/j.saa.2025.126146","article-title":"The enhanced\nexcited-state intramolecular proton transfer energy barrier of flavonols\ninduced by deprotonation","volume":"337","author":"Luo","year":"2025","journal-title":"Spectrochim. Acta,\nPart A"},{"key":"2026100109061404200_cit31","doi-asserted-by":"publisher","first-page":"707","DOI":"10.1007\/s10895-007-0222-0","article-title":"Acidichromism\nand ionochromism of luteolin and apigenin, the main components of\nthe naturally occurring yellow weld: A spectrophotometric and fluorimetric\nstudy","volume":"17","author":"Favaro","year":"2007","journal-title":"J. Fluoresc."},{"key":"2026100109061404200_cit32","doi-asserted-by":"publisher","first-page":"2863","DOI":"10.1021\/acs.jpcb.2c00929","article-title":"Photophysical Behavior\nof Plant Flavonols Galangin,\nKaempferol, Quercetin, and Myricetin in Homogeneous Media and the\nDMPC Model Membrane: Unveiling the Influence of the B-Ring Hydroxylation\nof Flavonols","volume":"126","author":"Sahu","year":"2022","journal-title":"J. Phys. Chem. B"},{"key":"2026100109061404200_cit33","doi-asserted-by":"publisher","first-page":"11328","DOI":"10.1021\/acs.jpcb.4c06452","article-title":"Fluorescence Enhancement\nof Nonemissive Monodeprotonated Luteolin\nin a Poly(vinyl alcohol) Film","volume":"128","author":"Wang","year":"2024","journal-title":"J. Phys. Chem.\nB"},{"key":"2026100109061404200_cit34","doi-asserted-by":"publisher","first-page":"2458","DOI":"10.1021\/acs.jpcb.5c08688","article-title":"Turning on\nthe Fluorescence of Flavonoid Anions: Synergistic Roles of Spatial\nConstraints and Microbasicity in Poly(vinyl alcohol)\/DMSO Films","volume":"130","author":"Li","year":"2026","journal-title":"J. Phys. Chem. B"},{"key":"2026100109061404200_cit35","doi-asserted-by":"publisher","first-page":"142724","DOI":"10.1016\/j.cplett.2026.142724","article-title":"The role of intermolecular hydrogen bonding on electronic excitation\nenergies of flavonoids","volume":"889","author":"Du","year":"2026","journal-title":"Chem. Phys. Lett."},{"key":"2026100109061404200_cit36","doi-asserted-by":"publisher","first-page":"923","DOI":"10.1039\/c8pp00053k","article-title":"Role of solute-solvent\nhydrogen bonds on the ground state and the excited state proton transfer\nin 3-hydroxyflavone. A systematic spectrophotometric study","volume":"17","author":"Lazzaroni","year":"2018","journal-title":"Photochem. Photobiol. Sci."},{"key":"2026100109061404200_cit37","unstructured":"Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al., Gaussian\n16, Revision A.03; Gaussian Inc.: Wallingford, CT, 2016."},{"key":"2026100109061404200_cit38","doi-asserted-by":"publisher","first-page":"6615","DOI":"10.1039\/b810189b","article-title":"Long-range\ncorrected hybrid density functionals with\ndamped atom\u2013atom dispersion corrections","volume":"10","author":"Chai","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026100109061404200_cit39","doi-asserted-by":"publisher","first-page":"51","DOI":"10.1016\/j.cplett.2004.06.011","article-title":"A new hybrid exchange-correlation\nfunctional using the Coulomb-attenuating method (CAM-B3LYP)","volume":"393","author":"Yanai","year":"2004","journal-title":"Chem. Phys. Lett."},{"key":"2026100109061404200_cit40","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 Suite of Density Functionals\nfor Main Group\nThermochemistry, Thermochemical Kinetics, Noncovalent Interactions,\nExcited States, and Transition Elements: Two New Functionals and Systematic\nTesting of Four M06-class Functionals and 12 Other Functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."}],"container-title":["The Journal of Physical\nChemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.6c04063","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/39\/10291\/68534421\/acs.jpcb.6c04063.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/39\/10291\/68534421\/acs.jpcb.6c04063.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T13:31:32Z","timestamp":1790861492000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/130\/39\/10291\/5431449\/Linear-Response-and-State-Specific-Polarizable"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,16]]},"references-count":40,"journal-issue":{"issue":"39","published-online":{"date-parts":[[2026,9,16]]},"published-print":{"date-parts":[[2026,10,1]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.6c04063","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,16]]}}}