eprintid: 8213 rev_number: 5 userid: 6 dir: disk0/00/00/82/13 datestamp: 2011-11-10 19:48:47 lastmod: 2016-11-15 13:45:10 status_changed: 2011-11-10 19:48:47 type: thesis_degree metadata_visibility: show contact_email: kad246@pitt.edu item_issues_count: 0 eprint_status: archive creators_name: Diri, Kadir creators_email: kad246@pitt.edu creators_id: KAD246 title: THEORETICAL STUDIES OF DIPOLE-BOUND ANIONS AND SMALL WATER CLUSTERS ispublished: unpub divisions: sch_as_chemistry full_text_status: public keywords: dipole-bound anions; water clusters abstract: Part I of this work deals with dipole-bound anions of moderately and highly polar molecules. High level electronic structure calculations are performed on nitrile, carbonate, and sulfite containing molecules. The results are compared against experimental data obtained from Rydberg electron transfer, photoelectron spectroscopy, and field detachment studies. Explanations to the unusual trends in the electron binding energies of the series of nitrile containing molecules are suggested. Calculation results also help in suggesting an explanation to the interesting dissociative electron attachment observed in ethylene sulfite. Part II of the thesis is devoted to theoretical studies of neutral and anionic water clusters. Neutral water clusters are important in establishing the bridge between a single water molecule and its bulk phase, while still allowing for accurate quantum mechanical calculations. Anionic water clusters on the other hand, are valuable species in the study of electron capture, solvation, and transfer, which are important chemical and biological processes. Here, we focus mainly on the energetic and spectroscopic features of water clusters. Namely, we consider the effects of anharmonicity and high-level electron correlation to the vibrational frequencies and to the binding energies of the (H2O)n, n = 2-6 neutral clusters. We also attempt to assign the vibrational spectrum of the (H2O)7-Arm cluster, which shows unusual complexity and Ar solvation dependence, when compared with smaller clusters. date: 2007-09-20 date_type: completed institution: University of Pittsburgh refereed: TRUE etdcommittee_type: committee_chair etdcommittee_type: committee_member etdcommittee_type: committee_member etdcommittee_type: committee_member etdcommittee_name: Jordan, Kenneth D. etdcommittee_name: Earl, David J. etdcommittee_name: Kim, Hyung J. etdcommittee_name: Siska, Peter E. etdcommittee_email: ken@visual1.chem.pitt.edu etdcommittee_email: dearl@pitt.edu etdcommittee_email: hjkim@cmu.edu etdcommittee_email: pes@pitt.edu etdcommittee_id: JORDAN etdcommittee_id: DEARL etdcommittee_id: etdcommittee_id: PES etd_defense_date: 2007-06-26 etd_approval_date: 2007-09-20 etd_submission_date: 2007-06-28 etd_access_restriction: 5_year etd_patent_pending: FALSE assigned_doi: doi:10.5195/pitt.etd.2011.8213 thesis_type: dissertation degree: PhD committee: Kenneth D. Jordan (ken@visual1.chem.pitt.edu) - Committee Chair committee: David J. Earl (dearl@pitt.edu) - Committee Member committee: Hyung J. Kim (hjkim@cmu.edu) - Committee Member committee: Peter E. Siska (pes@pitt.edu) - Committee Member etdurn: etd-06282007-130843 other_id: http://etd.library.pitt.edu/ETD/available/etd-06282007-130843/ other_id: etd-06282007-130843 citation: Diri, Kadir (2007) THEORETICAL STUDIES OF DIPOLE-BOUND ANIONS AND SMALL WATER CLUSTERS. Doctoral Dissertation, University of Pittsburgh. (Unpublished) document_url: http://d-scholarship-dev.library.pitt.edu/8213/1/diri_etd2007.pdf