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1、ViewOnlinePCCPDynamicArticleLinksCitethis:Phys.Chem.Chem.Phys.,2011,13,6670–6688www.rsc.org/pccpPAPERAthoroughbenchmarkofdensityfunctionalmethodsforgeneralmaingroupthermochemistry,kinetics,andnoncovalentinteractionswabaLarsGoerigkandStefanGrimme*Received28thD
2、ecember2010,Accepted10thFebruary2011DOI:10.1039/c0cp02984jAthoroughenergybenchmarkstudyofvariousdensityfunctionals(DFs)iscarriedoutwiththenewGMTKN30databaseforgeneralmaingroupthermochemistry,kineticsandnoncovalentinteractions[GoerigkandGrimme,J.Chem.Theor.Com
3、put.,2010,6,107;GoerigkandGrimme,J.Chem.Theor.Comput.,2011,7,291].Intotal,47DFsareinvestigated:twoLDAs,14GGAs,threemeta-GGAs,23hybridsandfivedouble-hybrids.Besidesthedouble-hybrids,alsoothermodernapproaches,i.e.,theM05andM06classesoffunctionalsandrange-separat
4、edhybrids,aretested.Foralmostallfunctionals,thenewDFT-D3correctionisappliedinordertoconsistentlytesttheperformancealsoforimportantnoncovalentinteractions;theparametersaretakenfrompreviousworksordeterminedforthepresentstudy.Basissetandquadraturegridissuesareal
5、soconsidered.Thegeneralaimofthestudyistoworkoutwhichfunctionalsaregenerallywellapplicableandrobusttodescribetheenergiesofmolecules.Insummary,werecommendontheGGAleveltheB97-D3andrevPBE-D3functionals.Thebestmeta-GGAisoTPSS-D3althoughmeta-GGAsrepresentingeneraln
6、oclearimprovementcomparedtonumericallysimplerGGAs.Notably,thewidelyusedB3LYPfunctionalperformsworsethantheaverageofalltestedhybridsandisalsoverysensitivetotheapplicationofdispersioncorrections.Wediscourageitsusageasastandardmethodwithoutcloserinspectionofther
7、esults,asitstillseemstobeoftendonenowadays.Surprisingly,long-rangecorrectedexchangefunctionalsdoingeneralnotperformbetterthanthecorrespondingstandardhybrids.However,theoB97X-Dfunctionalseemstobeapromisingmethod.ThemostrobusthybridisZhaoandTruhlar’sPW6B95Downl
8、oadedbyUniversityofScienceandTechnologyofChinaon09July2011Publishedon07March2011onhttp://pubs.rsc.org
9、doi:10.1039/C0CP02984JfunctionalincombinationwithDFT-D3.Ifhigheraccuracyisrequired,do
