?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%2F9728%2F&rft.title=HIGH+RESOLUTION+ELECTRONIC+SPECTROSCOPY+OF+NITROGEN-CONTAINING+MOLECULES+IN+THE+GAS+PHASE%3A+26DAP+AND+PYRBN&rft.creator=Clements%2C+Casey+Lynn&rft.description=High+resolution+gas+phase+electronic+spectra+were+recorded+for+2%2C6-diaminopyridine+(26DAP)+and+pyrrolidinobenzonitrile+(PYRBN).+A+comparison+of+the+electronic+properties+of+the+nitrogen-containing+rings+aniline%2C+2-aminopyridine%2C+and+2%2C6-diaminopyridine+(26DAP)+shows+that+the+potential+energy+surface+of+the+molecule+is+significantly+affected+as+more+nitrogen+atoms+are+added+to+the+system.+High+resolution%2C+rotationally+resolved+spectra+of+four+vibrational+bands+in+the+S1+-+S0+electronic+transition+of+26DAP+were+obtained+in+order+to+explain+these+changes.+The+zigzagging+inertial+defects+point+to+a+double+minimum+excited+state+potential+energy+surface+along+the+coupled+amino+group+inversion+vibrational+mode%2C+which+becomes+a+four-fold+well+(and+barrier)+problem+when+the+existence+of+two+nearly+degenerate+isomers+is+taken+into+account.+Assuming+that+the+molecules+are+in+the+lower+energy%2C+opposite-side+configuration%2C+ab+initio+calculations+were+performed+using+the+MP2%2F6-31G**+level+of+theory+to+create+a+potential+energy+surface+modeling+the+simultaneous+antisymmetric+NH2-inversion+mode.+The+calculated+potential+energy+surface+shows+a+ground+electronic+state+barrier+to+simultaneous+NH2+inversion+of+~+220+cm-1%2C+and+a+fit+to+experimental+vibrational+energy+level+spacings+and+relative+intensities+produces+an+excited+electronic+state+barrier+of+~+400+cm-1.+The+ground+state+barrier+is+less+than+that+in+aniline%2C+but+the+excited+state+barrier+is+larger.Pyrrolidinobenzonitrile+(PYRBN)%2C+a+derivative+of+DMABN%2C+has+been+examined+here+using+high+resolution+fluorescence+excitation+spectroscopy+in+the+presence+of+an+electric+field+varying+from+0+-+846+V%2Fcm.+The+b-type+fluorescence+band+reveals+that+the+transition+moment+is+along+the+short%2C+in+plane+axis+of+the+molecule.+Upon+excitation+the+inertial+defect+remains+unchanged%2C+which+suggests+that+the+molecule's+planarity+remains+constant.+The+dipole+moment+is+found+to+increase+from+8.06+to+10.45+D+upon+electronic+excitation.+This+analysis+of+PYRBN+leads+to+many+interesting+comparisons+to+1PP+including+their+transition+moments%2C+dipole+moments%2C+and+inertial+defects.&rft.date=2011-01-27&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%2F9728%2F1%2FCaseyClementsMSThesis.pdf&rft.identifier=++Clements%2C+Casey+Lynn++(2011)+HIGH+RESOLUTION+ELECTRONIC+SPECTROSCOPY+OF+NITROGEN-CONTAINING+MOLECULES+IN+THE+GAS+PHASE%3A+26DAP+AND+PYRBN.++Master's+Thesis%2C+University+of+Pittsburgh.++++(Unpublished)++