?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F35704%2F&rft.title=Computational+Studies+of+Structure+and+Surface+Reactivity+in+Metal+Nanoclusters&rft.creator=Hartmann%2C+Michael&rft.description=Metal+nanoparticles+exhibit+physical+and+chemical+properties+unique+to+their+length+scale+that+have+the+potential+to+shape+next+generation+technologies.+The+large+structural+and+chemical+space+that+determines+nanoparticle+properties+requires+feedback+between+computational+and+experimental+studies+to+drive+the+discovery+of+both+new+architectures+and+target+properties+of+these+systems.+This+dissertation+describes+the+application+and+development+of+theoretical+methods+to+study+metal+nanoparticle+electronic+structure%2C+developing+new+structure-property+relationships+and+new+concepts+that+govern+nanoparticle+behavior+while+connecting+theoretical+insight+with+laboratory+observations.%0D%0AIn+Chapter+1%2C+the+dissertation+is+introduced+by+detailing+how+the+connection+between+geometry+and+electronic+structure+has+shaped+the+way+we+teach+and+understand+chemistry+across+length+scale%2C+and+projects+these+concepts+onto+the+1-3+nm+length+scale+where+traditional+descriptors+of+electronic+structure+break+down.+In+Chapter+2%2C+the+optoelectronic+impact+of+alloying+Cu+with+a+Au+nanocluster+is+studied%2C+revealing+how+atomic+descriptors+and+position+of+the+heteroatom+determine+optical+absorption+in+%5BAu25(SR)18%5D+%2C+providing+an+easily+accessible+experimental+readout+of+electronic+structure.+Building+on+hypotheses+tested+in+Chapter+2%2C+Chapter+3+explores+the+size+dependence+of+Cu%2FAu+alloying.+Here%2C+the+atom+concentration+and+composition+architecture+are+key+parameters+predicted+to+drive+the+emergence+of+plasmonic+behavior+in+Au144-xCux(SR)60+nanocluster.%0D%0AIn+addition+to+the+composition+dependence+of+nanoparticle+properties%2C+the+surface+chemistry+is+known+to+dominate+overall+nanocluster+electronic+structure.+In+Chapter+4%2C+both+the+type+and+specific+molecular+descriptors+of+the+ligand+were+shown+to+impact+the+total+magnetic+moment+of+Co13+and+Co55+model+nanoclusters.+Chapter+5+extends+these+concepts+of+surface+chemistry+to+address+the+size+dependent+evolution+of+the+ligand+mediated+magnetic+properties+in+CoN+nanoclusters%2C+demonstrating+how+energy+level+alignment+and+orbital+symmetry+contribute+to+size+dependent+trends.+Finally%2C+Chapter+6+describes+a+reduced+scaling+computational+method+that+improves+the+approximation+of+mean+field+excited+state+energy+predictions%2C+increasing+the+size+and+complexity+of+systems+that+can+be+treated+with+high+accuracy.&rft.date=2019-01-30&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F35704%2F7%2Fhartmannmj_ETD_final_resubmit.pdf&rft.identifier=++Hartmann%2C+Michael++(2019)+Computational+Studies+of+Structure+and+Surface+Reactivity+in+Metal+Nanoclusters.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++