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1、J.Phys.Chem.B2002,106,3979-39863979ChlorideIonHydrationandDiffusioninSupercriticalWaterUsingaPolarizableWaterModelMasahitoKubo,²RonaldM.Levy,*,³PeterJ.Rossky,§NobuyukiMatubayasi,
2、andMasaruNakahara*,
3、DepartmentofChemistryandChemicalBiology,Rutgers,TheStateUniVersityofNew
4、Jersey,Piscataway,NewJersey08854-8087,InstituteforTheoreticalChemistry,DepartmentofChemistryandBiochemistry,UniVersityofTexasatAustin,Austin,Texas78712,andInstituteforChemicalResearch,KyotoUniVersity,Uji,Kyoto611-0011,JapanReceiVed:October8,2001;InFinalForm:February11,2
5、002Chlorideionsolvationinsupercriticalwaterisinvestigatedbycomputersimulations,includingwaterpolarizabilityexplicitly.ComparisonsaremadebetweentheTIP4PfluctuatingchargeandtheoriginalTIP4Pmodels.Particularattentionispaidtothedensitydependenceoftheequilibriumstructuraland
6、transportproperties.Thechlorideionhydrationnumberslowlydecreaseswithdensityreductioninasimilarwayforboththefluctuatingchargeandthefixed-chargewatermodels.Thediffusioncoefficientsforthetwomodelsalsoexhibitasimilardensitydependence,exceptatthelowestdensityexamined(0.05g/c
7、m3),wherethechlorideiondiffusionrateinpolarizablewaterissignificantlylargerthanthatinnonpolarizablewaterbecauseofamorerapidlossofthehydrationshellinpolarizablewateratthelowestdensity.Theremarkablesimilaritybetweenthetwomodelsisrelatedtotheinsensitivityofthelocalpolariza
8、tioninthefirsthydrationshelltothebulkconditions.Theresultsalsosuggestthatthelocalviscosityratherthanthelong-rangedielectricfrictiondominatesthetransportproperties.1.Introductionsimulation,primarilyusingnonpolarizablemodels.8-14Assimplifiedyetpowerfultools,nonpolarizable
9、modelsareusuallyMostcommonchemicalandbiologicalprocessesthatinvolveparametrizedtoreproducemanystructural,thermodynamic,andsolvationoccuratornearroomtemperatureandatmosphericdynamicpropertiesintheliquidphaseatambientconditions.pressure.Inrecentyears,however,therehasbeeni
10、ncreasingUnderextremeconditions,supercriticalorsubcritical,theseinterestinsupercriticalfluidsolutions.Thesuper
