?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%2F23741%2F&rft.title=Theoretical+and+Experimental+Explorations+of+Charge+Transfer+in+Small+Molecules+and+Peptide+Nucleic+Acids&rft.creator=Xing%2C+Yin&rft.description=Non-adiabatic+charge+transfer+(CT)+is+one+of+the+simplest+but+very+important+(if+not+the+most+important)+chemical+reactions.+As+a+model+system%2C+alkanedithiols+are+among+the+most+popular+ones+for+short-+or+medium-range+CT.+Peptide+nucleic+acids+(PNAs)%2C+which+consist+of+nucleobases+but+with+peptide+backbones+instead+of+the+phosphate+backbones+in+DNA%2C+is+another+promising+model+system+for+long-range+CT.+Various+models+and+computational+methods+have+been+developed+to+describe+three+major+experimental+configurations%3A+electrochemical+measurement+with+self-assembled+monolayer+films+(SAMs)%2C+single-molecule+conductance+measurement+and+photoinduced+electron+transfer+(PET).%0D%0A%0D%0AThis+dissertation+have+employed+above+experimental+techniques+and+computational+methods+to+study+the+two+model+systems.+The+first+work+focuses+on+electrochemical+models.+Single-step+models+are+widely+used+for+analyzing+CT+through+SAMs.+However%2C+long-range+CT+can+occur+in+a+%E2%80%9Chopping%E2%80%9D+regime+that+involves+multiple+events.+This+study+describes+a+three-step+kinetic+scheme+to+model+CT+in+this+regime.+It+is+corroborated+by+the+experimental+results+of+a+10-mer+peptide+nucleic+acid+SAM.+The+second+study+compares+single+molecule+conductances+of+alkanedithiols+and+alkoxydithiols.+Both+molecular+junction+measurements+and+theoretical+simulations+by+non-equilibrium+Green%E2%80%99s+function+(NEGF)+method+show+that+the+conductance+is+lower+for+alkoxydithiols+and+the+difference+is+length+dependent.+A+pathway+analysis+of+the+electronic+coupling+is+used+to+explain+the+results.+The+last+two+studies+address+the+importance+of+conformational+distributions+on+charge+transfer+in+PNAs%3A+The+third+study+compares+the+electrochemical+charge+transfer+rates+of+normal+aeg-PNA+and+%CE%B3-PNA+which+has+a+less+flexible+backbone.+Molecular+dynamics+and+NEGF+calculations+show+that+the+greater+flexibility+of+the+aeg-PNA+gives+rise+to+a+more+frequent+appearance+of+high-CT+rate+conformations.+In+the+last+study+a+new+PNA+scaffold+with+a+%5BRu(Bpy)3%5D2%2B+donor+and+a+bis(8-hydroxyquinolinate)2+copper+acceptor+for+PET+is+described.+Experiments+show+that+whether+the+%5BRu(Bpy)3%5D2%2B+is+terminally+or+centrally+situated+affects+PET.+Molecular+dynamics+simulations+reveal+that+the+difference+in+conformational+distributions+is+a+possible+explanation.+The+findings+in+these+studies+provide+a+deeper+understanding+of+CT+in+molecules%2C+and+may+facilitate+the+development+of+non-adiabatic+dynamics+in+a+bigger+picture.%0D%0A&rft.date=2015-01-14&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%2F23741%2F1%2FETD_XYin.F3_1.pdf&rft.identifier=++Xing%2C+Yin++(2015)+Theoretical+and+Experimental+Explorations+of+Charge+Transfer+in+Small+Molecules+and+Peptide+Nucleic+Acids.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++