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1、J.Phys.Chem.A2004,108,10865-1087210865PropertiesoftheC-HâââHDihydrogenBond:AnabInitioandTopologicalAnalysisPaweøLipkowski,²,³SøawomirJ.Grabowski,*,²,§TeriL.Robinson,²andJerzyLeszczynski²ComputationalCenterforMolecularStructureandInteractions,DepartmentofChemistry,JacksonStateUniVersity,
2、Jackson,Mississippi39217,InstituteofPhysicalandTheoreticalChemistry,WrocøawUniVersityofTechnology,Wyb.WyspianÂskiego27,50-370Wrocøaw,Poland,andDepartmentofCrystallographyandCrystalChemistry,UniVersityofèoÂdzÂ90-236èoÂdzÂ,ul.Pomorska149/153,PolandReceiVed:April2,2004;InFinalForm:Septembe
3、r29,2004Thedihydrogen-bondedcomplexesofmethaneanditsfluoroandchloroderivativeswithlithiumhydrideareanalyzedusingabinitiomethodsaswellastheBadertheory.AllcalculationswereperformedusingPople'sbasissets(6-311++G(d,p),6-311++G(2df,2pd),and6-311++G(3df,3pd))andtheDunningbases(aug-cc-pVDZanda
4、ug-cc-pVTZ)withintheMP2method.Theresultsofthecalculationsshowthatthebindingenergyfortheanalyzedcomplexesincreaseswiththeincreaseofthenumberoffluoroorchlorosubstituents,upto7kcal/mol.Inthesameorderthereisanincreaseoftheelectrostaticenergyterm,showingthatfortheCF3HâââHLicomplexthedihydro
5、genbondinteractionissimilarinnatureasforthewaterdimerwhereaconventionalO-HâââOhydrogenbondexists,whilefortheCCl3HâââHLidimertheexchangeenergytermoutweighstheelectrostaticenergy.Hence,theotherattractiveenergytermsareimportant.AtopologicalanalysisbasedontheBadertheorysupportstheresultsoft
6、heabinitiocalculationssincetheelectrondensitiesattheHâââHbondcriticalpointsandtheothertopologicalparametersaresimilartothosecalculatedformoderateconventionalhydrogenbonds.IntroductionAlkortaetal.werethefirsttoapplytopologicalanalysestoDHBs.11Theyfoundforthesampleofthefollowingcomplexes,
7、Duringthe1990sanewtypeofinteractionnameddihydrogen-âââHCN,BH-+bond1(DHB)wasdetectedformetalorganiccrystalstructures.2,3BH44âââCH4,LiHâââNH4,LiHâââHCN,LiHâââHCCH,BeH2âââNH4+,BeH2âââHCN,andCH4âââNH4+,thattheThisinteractionwasdesignatedasX-HâââH-M,whereX-HelectrondensityattheHâââH
