基于第一性原理和量子動(dòng)力學(xué)研究有機(jī)體系中電子轉(zhuǎn)移過(guò)程.pdf

1、中國(guó)科學(xué)技術(shù)大學(xué)博士學(xué)位論文基于第一性原理和量子動(dòng)力學(xué)研究有機(jī)體系中電子轉(zhuǎn)移過(guò)程姓名：張偉偉申請(qǐng)學(xué)位級(jí)別：博士專業(yè)：物理化學(xué)指導(dǎo)教師：趙儀20100501AbstractABSTRACTTwokindsofelectrontransfer(ET)processesindifferentorganicsystemsareinvestigatedbasedonfirstprinciplesandquantumdynamicsmethodsO

2、neistheintramolecularETreactioninsolution，theotheristhechargetransportinorganicsemiconductorFortheintramolecularETreactioninsolution，wetakeachargelocalizedintervalenceradicalcationofabis(hydrazine)asanexampleAvarietyofab

3、initioapproachesareemployedtocalculateETparameters，reorganizationenergy，electroniccouplingandeffectivefrequency，andtheirvalidityarealsodiscussedforthissystemWithuseoftheobtainedparameters，theextendSumi—Marcusreaction—dif

4、fusiontheoryisadoptedtopredicttheETratesTheresultsmanifestthattheETratesofthreeisomersareagreementwiththeESRexperimentquitewellwhiletherateoftheleftoneisabout1000timeslargerthantheexperimentaloneBecauseofthelimitationofE

5、SRexperiment，thislargeratecannotbemeasuredThus，oneexpectsthatnewtechniqueshavetobeusedtofurtherinvestigateitForthechargetransportinorganicsemiconductor，wehaveinvestigatednonCondoneffectonthechargecarriermobilityoforganic

6、semiconductordithophenetetrathiathiafulvalene(DTTTF)crystalThefirstprinciplescalculationsrevealthatonlyseveralhighfrequencyintramolecularmodesdominatethereorganizationenergyThenuclear—coordinatedependenceofelectroniccoup

7、lingpreferstoperformanexponentialorGaussianpropertyformostintermolecularmodesratherthanalinearoneAtthesametime，theelectroniccoupling，whichiscalculatedwiththereducedtwostatemodel，ofanisolatedDTTTFdimerisindeedaffectedbyth

8、esurroundingmoleculesUnderthehoppingmechanismwiththenucleartunnelingincorporated，themobilitydisplaysthebandlikepropertyThepredictednonCondonmobilityisalwaysgreaterthanthatfromCondonapproximationFurthermore，wefindthatthen