?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%2F39494%2F&rft.title=USING+ULTRAFAST+VIBRATIONAL+SPECTROSCOPY+FOR+A+COMPREHENSIVE+UNDERSTANDING+OF+STRUCTURAL+AND+ROTATIONAL+MOTIONS+FOR+WATER+TO+PROTIC+IONIC+LIQUIDS&rft.creator=Johnson%2C+Clinton&rft.description=In+this+work%2C+two-dimensional+infrared+(2D-IR)+spectroscopy+investigates+the+timescale+of+solvent+fluctuations+for+proton+and+hydride+transfers.++To+elucidate+hydride+transfer+dynamics%2C+the+BH+stretch+of+%5Cce%7BBH4-%7D+is+probed+in+various+solvents+from+%5Cce%7BH2O%7D+to+ionic+liquids+(ILs).++For+proton+transfer+dynamics%2C+a+vibrational+probe+(%5Cce%7BSCN-%7D)+explores+the+three-dimensional+hydrogen+bonding+environment+of+a+protic+ionic+liquid+(PIL).++++%0D%0A+%0D%0A%5Cce%7BBH4-%7D+is+first+investigated+in+increasing+NaOH+concentrations+to+develop+a+molecular+understanding+of+suppressing+the+hydrogen+evolution+reaction.++As+the+concentration+increases%2C+the+timescale+of+frequency+fluctuations+decrease.++Born+Oppenheimer+molecular+dynamics+(BOMD)+simulations+suggest+that+a+crowding+effect+of+ions+around+%5Cce%7BBH4-%7D+inhibits+the+rearrangement+of+dihydrogen+bonds+between+%5Cce%7BBH4-%7D+and+%5Cce%7BH2O%7D.++To+completely+suppress+the+hydrogen+evolution+reaction%2C+ILs+with+%5Cce%7BBH4-%7D+as+the+anion+are+investigated.++The+linear+and+2D-IR+spectra+of+the+antisymmetric+BH+stretch+of+%5Cce%7BBH4-%7D+are+complicated+due+to+Fermi+resonances.++The+narrow+linear+and+2D-IR+linewidths+of+%5Cce%7BBH4-%7D+in+an+IL+allow+a+comprehensive+assignment+of+all+diagonal+peaks+and+crosspeaks.++Confirmed+with+a+model+Hamiltonian%2C+two+anharmonicities+for+the+antisymmetric+BH+stretch+of+%5Cce%7BBH4-%7D+are+characterized.+++++%0D%0A%0D%0APolarization-+and+temperature-dependent+2D-IR+is+employed+to+investigate+the+hydrogen+bonding+network+of+the+PIL+ethyl-ammonium+nitrate+(EAN).++%5Cce%7BSCN-%7D+experiences+two+hydrogen+bonding+subensembles+in+EAN+as+two+separate+vibrational+relaxation+times+are+resolved.++Furthermore%2C+the+polarization-weighted+frequency+fluctuation+correlation+function+can+be+separated+into+two+components%3A+structural+spectral+diffusion+(SSD)+and+reorientation-induced+spectral+diffusion+(RISD).++For+%5Cce%7BSCN-%7D+in+EAN%2C+the+timescales+of+frequency+fluctuations+are+in+the+rotational+limit+as+the+SSD+is+unresolved.++Temperature-dependent+2D-IR+extracts+the+enthalpy+and+entropy+of+activation+for+frequency+fluctuations.+For+%5Cce%7BSCN-%7D+in+EAN%2C+the+enthalpy+of+activation+for+rotational+motions+are+similar+as+to+%5Cce%7BSCN-%7D+in+%5Cce%7BH2O%7D%2C+and+this+suggests+that+the+breaking+and+forming+of+hydrogen+bonds+around+%5Cce%7BSCN-%7D+undergoes+a+similar+mechanism+in+EAN+as+in+%5Cce%7BH2O%7D.&rft.date=2020-09-16&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%2F39494%2F19%2FJohnson%2520Final%2520ETD.pdf&rft.identifier=++Johnson%2C+Clinton++(2020)+USING+ULTRAFAST+VIBRATIONAL+SPECTROSCOPY+FOR+A+COMPREHENSIVE+UNDERSTANDING+OF+STRUCTURAL+AND+ROTATIONAL+MOTIONS+FOR+WATER+TO+PROTIC+IONIC+LIQUIDS.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++