大環(huán)釕系雙金屬配合物結(jié)構(gòu)和金屬多重鍵理論研究.pdf

1、分類號UDC密級壘開多毋廬夕擎碩士研究生學(xué)位論文大環(huán)釕系雙金屬配合物結(jié)構(gòu)和金屬多重鍵理論研究申請人0學(xué)號：培養(yǎng)單位：學(xué)科專業(yè)：研究方向：指導(dǎo)教師：完成日期：呂金宇2131144黑龍江大學(xué)物理化學(xué)應(yīng)用量子化學(xué)潘清江教授2016年3月26臼AbstractAbstractInthisthesis，ruthenium—groupporphyrazinesincludingmonomerdimerandpyridine—solvatedderi

2、vativeshavebeenexaminedusinghybriddensityfunctionaltheory(DFT)，thequasi—relativisticeffectivecorepotentials(ECPs)aswellasexplicitandimplicitsolvationRegardingourinvestigatedsystems，weexploredFe，RuandOs(d6electronconfigur

3、ation)；porphyrazine(1abeledasPz)ligandwasused，whichalsocanapproximatelyrepresentporphyrin(Por)andphthalocyanine(Pc)thatarecommonlyusedinexperiment；Researchsystemincludingmultipleelectronicspinstates”isomer”suchas(Rupz)2i

4、nd6d6effects，canbeformedfiveelectronicstatesfromsinglettononetstates；additionallydimerandsolvatedderivativecanadoptbotheclipsedandstaggeredconfigurationsThestructureoptimizationandenergycalculationshowthatthedimer(RuPz)2

5、isl／lorestableinenergythanitsmonomer(RuPz)，thestaggeredconfigurationbetweentwoPzligandsrelativetoRu—RuaxisdirectionisenergeticallyfavoredThestaggeredtripletstate(RuPz)2wascalculatedastheglobalgroundstate，consistentwithth

6、eexperimentalresultsCompleteactivespaceselfconsistentfield(CASSCF)and珂electronvalencestatesecond—orderperturbationtheory(NEVPT2、supportedtheDFTresults，andfurtherconfirmedtheRu2doublebondiscomposedofoned6andonedxbondsTheR

7、u—Rubondingenergywascalculatedtobe307kcal／molwhileconsideringthebasissetsuperpositionerror(BSSE)Theelectronicabsorptionspectrainpyridinesolutionwerecalculatedbythetimedependentdensityfunctionaltheory(TDDFT)onthebasisofth

8、eoptimizedstructuresof(RuPz)‘PY2and(RuPz)2‘pY2ApronouncedredshiftofmajorabsorptionbandsisfoundinthelattercomparedwiththeformeLExperimentalobservationoftheredshiftofabsorptionspectrauponincreasingthesolutionconcentrationw

9、aswellreproducedbythepresentcalculationsThecomplexes(M。1Pz)，(MPz)2and(MPz)PY2(M=FeandOs)werealsoexploredintheoryItisshownthat(OsPz)2hasthesingletglobalgl‘oundstateTheOs—Osdoublebond，composedofonedaandonedltbonds，wasassig