六卟啉[1.0.1.0.0.0]及其衍生物与锕系酰离子间相互作用的密度泛函理论研究-density functional theory study on the interaction between hexaporphyrin [ 1.0.1.0.0.0 ] and its derivatives and actinide ions.docxVIP
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六卟啉[1.0.1.0.0.0]及其衍生物与锕系酰离子间相互作用的密度泛函理论研究-density functional theory study on the interaction between hexaporphyrin [ 1.0.1.0.0.0 ] and its derivatives and actinide ions
四川师范大学硕士学位论文究了它们与uo+的配合物的性质。结果显示,磷酸化能够有效增加氨基酸与UO:的结合能力,同时还能利用其所带的高电负性基团形成氢键网络,使体系得到稳定。关键词DFT铀酰钚酰大环配体isoamethyrin丝氨酸磷酸化万方数据AbstractADFTStudyonInteractionbetweenactinylsand---●一isoamethyrinanologuesPhysicalChemistryByFuwanZhaiSupervisedbyProf.LaicaiLiAbstractAstheincreasingdemandandconsumptionofenergy,issuesrelatedtoenvironment,economicandpolicyhavebeenaroused.Thenuclearenergysystem,whichhasbeenfoundfordecades,hasbeenanewpathtoenergyforhumanbeings.Investigationandutilizationofnuclearenergyhasbeenyears,however,thedisposalofspentfuelsremainsaschallengetothestateoftheart.VarietyofextractantsaredevelopedtoseparateelementsofdissolvedfuelrodsandPUREXprocessareimplementedindustrially.However,thedefectsofTBPandanyotherextractantsstudieddriveandinspireresearcherstodesignnewerandmoreefficientligandsforactinides.Formeettherequirementofdevelopmentofnewextractant,wehavepickedtheisoamethyrinasligandbecauseofthepre-organizationofmacrocycleligandandtheN.donorofit.ADFwasemployedtodealwithactinyl-containingcomplexesofisoarnethyrinanditsderivativeswhichobtainedbymodifyingthemacrocyclewithaseriesofsubstituentsusingrelativisticdensityfunctionaltheorywithafinecalculationprocedure.Theresultsobtainediscomparabletothatofexperiment.Furtheranalysis,e.g.NBO,AIM,TBE,wereperformedontheoptimizedgeometrytogetinformationinsidethebondingbetweenactinylandnitrogenatoms.Resultsshowthatallthecomplexesofplutonylresemblethatofuranylthatadoptbentgeometry.AllthebondaremoreionicthancovalentbecausethebondorderiSsmallerthan1anddensityatBCPiSsmallerthan0.1whereasthecovalentinteractionaugmentedwiththegraduallyheightenedtortuosityofcoordinationplane.Thereare10%moreoffcomponentinNBOformedbetweennitrogenanduranylthanthatbetweennitrogenandplutonylwhichgiverisetothereductionofligand.metalinteractioninplutonyl-containingcomplexes.AnalyzingwithTBEmethod,thebondingcharactersbetweenactinylandnitrogenareprovedtobeionicwhichisconsistenttothe万方数据四川师范大学硕士学位论文NBOandAIManalysis.Byalldatathatobtained,complexUL4isfoundtobetheonein
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