?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%2F22711%2F&rft.title=Vibrational+Anharmonicity+in+the+Water-Nitrate+Complex%2C+Ice%2C+and+Gas+Hydrates%3A+Applications+to+Spectroscopy+and+Thermal+Transport&rft.creator=Kratz%2C+Eric+G.&rft.description=Vibrational+anharmonicity+strongly+influences+the+properties+of+gas-phase+complexes+and+solids.+Anharmonicity+is+responsible+for+the+observation+of+%E2%80%9Cforbidden%E2%80%9D+vibrational+transitions%2C+thermal+expansion%2C+and+phonon-phonon+scattering.+In+the+first+portion+of+this+dissertation+the+vibrational+spectra+of+%5B(NO3-)(H2O)%5D+and+its+isotopologues+are+examined+through+effective++Hamiltonian+and+vibrational+configuration+interaction++calculations+employing+ab+initio+force+constants.+While+a++harmonic+treatment+of+the+%5B(NO3-)(H2O)%5D+infrared+absorption+spectrum+predicts+two+OH+stretch+transitions%2C+four+strong%0D%0Apeaks+are+experimentally+observed.+Anharmonic+vibrational+calculations+confirm+that+the+%E2%80%9Cextra%E2%80%9D+transitions+are+due+to+the+rocking+motion+of+the+water+molecule+relative+to+the+nitrate+ion+and+a+Fermi+resonance+between+the+OH+stretch+and+water+bend+overtone.+The+second+part+of+the+dissertation+explores+the+nature+of+the+vibrational+anharmonicity+of+gas+hydrates+and+ice+Ih+as+well+as+its+effects+on+the+structure+and+thermal+conductivity.+The%0D%0Aarrangement+of+the+hydrogen+atoms+in+the+solids+and+the+gas-water+interactions+are+found+to+have+a+strong+influence+on+some+of+the+properties+of+the+crystals.+Coarse-grained+simulations+and+analytic+scattering+approximations+qualitatively+reproduce+the+observed+behavior+of+the+thermal+conductivity+of+gas+hydrates+and+ice.+In+addition%2C+the+calculations+reveal+that+guest-host+coupling+cannot+fully+explain+the+differences+in+the+thermal+conductivity+of+gas+hydrates+and+ice.&rft.date=2014-09-23&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%2F22711%2F1%2FEric_Kratz_Dissertation.pdf&rft.identifier=++Kratz%2C+Eric+G.++(2014)+Vibrational+Anharmonicity+in+the+Water-Nitrate+Complex%2C+Ice%2C+and+Gas+Hydrates%3A+Applications+to+Spectroscopy+and+Thermal+Transport.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++