000207284 001__ 207284 000207284 005__ 20250730145754.0 000207284 0247_ $$2doi$$a10.1039/c3sc52862f 000207284 0247_ $$2ISSN$$a2041-6520 000207284 0247_ $$2ISSN$$a2041-6539 000207284 0247_ $$2WOS$$aWOS:000334492700006 000207284 0247_ $$2openalex$$aopenalex:W2167161800 000207284 037__ $$aPUBDB-2015-01267 000207284 041__ $$aEnglish 000207284 082__ $$a540 000207284 1001_ $$0P:(DE-HGF)0$$aHub, Jochen S.$$b0 000207284 245__ $$aThermodynamics of Hydronium and Hydroxide Surface Solvation 000207284 260__ $$aCambridge$$bRSC$$c2014 000207284 3367_ $$00$$2EndNote$$aJournal Article 000207284 3367_ $$2DRIVER$$aarticle 000207284 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1443102188_26512 000207284 3367_ $$2BibTeX$$aARTICLE 000207284 500__ $$a(c) The Royal Society of Chemistry 000207284 520__ $$aThe concentration of hydronium and hydroxide at the water–air interface has been debated for a long time. Recent evidence from a range of experiments and theoretical calculations strongly suggests the water surface to be somewhat acidic. Using novel polarizable models we have performed potential of mean force calculations of a hydronium ion, a hydroxide ion and a water molecule in a water droplet and a water slab and we were able to rationalize that hydronium, but not hydroxide, is slightly enriched at the surface for two reasons. First, because the hydrogen bond acceptance capacity of hydronium is weaker than water and it is more favorable to have the hydronium oxygen on the surface. Second, hydroxideions are expelled from the surface of the droplets, due to the entropy being lower when a hydroxide ion is hydrated on the surface. As a result, the water dissociation constant pKw increases slightly near the surface. The results are corroborated by calculations of surface tension of NaOH solutions that are in reasonable agreement with the experiment. The structural and thermodynamic interpretation of hydronium and hydroxide hydration provided by these calculations opens the route to a better understanding of atmospheric and surface chemistry. 000207284 536__ $$0G:(DE-H253)POF2-CFEL-Exp.-20130405$$aExperiments at CFEL (POF2-544)$$cPOF2-544$$fPOF II$$x0 000207284 588__ $$aDataset connected to CrossRef, bib-pubdb1.desy.de 000207284 693__ $$0EXP:(DE-H253)CFEL-Exp-20150101$$5EXP:(DE-H253)CFEL-Exp-20150101$$eExperiments at CFEL$$x0 000207284 7001_ $$0P:(DE-HGF)0$$aWolf, Maarten G.$$b1 000207284 7001_ $$0P:(DE-H253)PIP1011740$$aCaleman, Carl$$b2 000207284 7001_ $$0P:(DE-HGF)0$$avan Maaren, Paul J.$$b3 000207284 7001_ $$0P:(DE-HGF)0$$aGroenhof, Gerrit$$b4 000207284 7001_ $$0P:(DE-HGF)0$$avan der Spoel, David$$b5$$eCorresponding author 000207284 773__ $$0PERI:(DE-600)2559110-1$$a10.1039/c3sc52862f$$gVol. 5, no. 5, p. 1745 -$$n5$$p1745 - 1749$$tChemical science$$v5$$x2041-6539$$y2014 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.pdf$$yRestricted 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf.pdf$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf_supp.pdf$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf.gif?subformat=icon$$xicon$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf.jpg?subformat=icon-180$$xicon-180$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf.jpg?subformat=icon-700$$xicon-700$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf.pdf?subformat=pdfa$$xpdfa$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf_supp.gif?subformat=icon$$xicon$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf_supp.jpg?subformat=icon-180$$xicon-180$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf_supp.jpg?subformat=icon-700$$xicon-700$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/hyd-pmf_supp.pdf?subformat=pdfa$$xpdfa$$yOpenAccess 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.gif?subformat=icon$$xicon$$yRestricted 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.jpg?subformat=icon-1440$$xicon-1440$$yRestricted 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.jpg?subformat=icon-180$$xicon-180$$yRestricted 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.jpg?subformat=icon-640$$xicon-640$$yRestricted 000207284 8564_ $$uhttps://bib-pubdb1.desy.de/record/207284/files/10.1039_C3SC52862F.pdf?subformat=pdfa$$xpdfa$$yRestricted 000207284 909CO $$ooai:bib-pubdb1.desy.de:207284$$pdnbdelivery$$pdriver$$pVDB$$popen_access$$popenaire 000207284 9101_ $$0I:(DE-588b)2008985-5$$6P:(DE-H253)PIP1011740$$aDeutsches Elektronen-Synchrotron$$b2$$kDESY 000207284 9101_ $$0I:(DE-H253)_CFEL-20120731$$6P:(DE-H253)PIP1011740$$aCentre for Free-Electron Laser Science$$b2$$kCFEL 000207284 9132_ $$0G:(DE-HGF)POF3-621$$1G:(DE-HGF)POF3-620$$2G:(DE-HGF)POF3-600$$9G:(DE-HGF)POF3-6211$$aDE-HGF$$bForschungsbereich Materie$$lVon Materie zu Materialien und Leben$$vIn-house research on the structure, dynamics and function of matter$$x0 000207284 9131_ $$0G:(DE-HGF)POF2-544$$1G:(DE-HGF)POF2-540$$2G:(DE-HGF)POF2-500$$3G:(DE-HGF)POF2$$4G:(DE-HGF)POF$$9G:(DE-H253)POF2-CFEL-Exp.-20130405$$aDE-H253$$bStruktur der Materie$$lForschung mit Photonen, Neutronen, Ionen$$vIn-house Research with PNI$$x0 000207284 9141_ $$y2014 000207284 915__ $$0StatID:(DE-HGF)0100$$2StatID$$aJCR 000207284 915__ $$0StatID:(DE-HGF)0110$$2StatID$$aWoS$$bScience Citation Index 000207284 915__ $$0StatID:(DE-HGF)0111$$2StatID$$aWoS$$bScience Citation Index Expanded 000207284 915__ $$0StatID:(DE-HGF)0150$$2StatID$$aDBCoverage$$bWeb of Science Core Collection 000207284 915__ $$0StatID:(DE-HGF)0199$$2StatID$$aDBCoverage$$bThomson Reuters Master Journal List 000207284 915__ $$0StatID:(DE-HGF)0300$$2StatID$$aDBCoverage$$bMedline 000207284 915__ $$0StatID:(DE-HGF)0310$$2StatID$$aDBCoverage$$bNCBI Molecular Biology Database 000207284 915__ $$0StatID:(DE-HGF)1150$$2StatID$$aDBCoverage$$bCurrent Contents - Physical, Chemical and Earth Sciences 000207284 915__ $$0StatID:(DE-HGF)9905$$2StatID$$aIF >= 5 000207284 915__ $$0StatID:(DE-HGF)0510$$2StatID$$aOpenAccess 000207284 9201_ $$0I:(DE-H253)FS-CFEL-1-20120731$$kFS-CFEL-1$$lCFEL-Coherent X-Ray Imaging$$x0 000207284 980__ $$ajournal 000207284 980__ $$aVDB 000207284 980__ $$aUNRESTRICTED 000207284 980__ $$aI:(DE-H253)FS-CFEL-1-20120731 000207284 9801_ $$aFullTexts