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1、13442J.Phys.Chem.A2010,114,1344213444CommentontheCorrectUseofContinuumcontributionsfromnuclearmotionofthesystem(i.e.,translation,SolventModelsrotation,andvibration)areidenticalorverysimilarinboththegasandthesolutionphasesuchthatappreciablecancellationisJunmingHo,AndreasKlamt,,§andexpe
2、cted.However,forthevariousreasonshighlightedinpointMichelleL.Coote*,2ofthiscommentary,includingthebreakdownoftheidealgasassumptioninsolution,thisassumptionisunlikelytobecorrect.ARCCentreofExcellenceforFree-RadicalChemistryandAsaresult,anynoncancelingdifferencesinthethermalBiotechnolog
3、y,ResearchSchoolofChemistry,Australiancontributionsinthetwophases(e.g.,entropicchangesassociatedNationalUniVersity,CanberraACT0200,Australia,withstructuralreorganizationofthesolvent)areindirectlyCOSMOlogicGmbH&CoKG,BurscheiderStr.515,incorporatedinto(Esoln+Gnes)throughparametrizationo
4、feq351381LeVerkusen,Germany,andInstituteofPhysicalandtoreproduceexperimentalsolvationfreeenergies.TheoreticalChemistry,UniVersityofRegensburg,Inthislight,itfollowsfromcomparisonofeqs3and2that93040Regensburg,Germanytheexpressionforthefreeenergyinsolutionis,ratherReceiVed:July30,2010;Re
5、VisedManuscriptReceiVed:counterintuitively,givenbyeq4.October13,2010Gsoln)Esolv+Gnes+∆Gcorr_gas(4)Thedevelopmentofdielectriccontinuumsolventmodels1,2(CSMs)hasfacilitatedthestudyofchemicalreactionsinthewhere∆Gcorr_gasreferstothethermalcorrectiontothefreecondensedphaseinacomputationally
6、efficientmanner.Theseenergyofthesoluteinthegasphase,notthesolutionphase.methodshavebeenparametrizedtodeliveraccuratevaluesofFurthermore,whenoneneedstocalculatethesolvationenergythefreeenergiesofsolvation,whichcanbeaddedtoaccuratebycombiningtheresultsofseparategas-andsolution-phasevalue
7、softhefreeenergiesinthegas-phase,toobtainthecalculations,onemustuseitsdefinitionwithintheCSMcorrespondingsolution-phasefreeenergy:framework,eq3,ratherthanthestandardtextbookdefinition,eq2.TheseresultswillholdwheneveraCSMisparametrizedRTaccordingtoeq3,irrespectiveofthesoftwareusedtocalcu
8、lateG
