Intramolecular interactions in rhodium monoxide and halogen azides
| dc.contributor.author | Jensen, Roy Henry | |
| dc.contributor.supervisor | Balfour, Walter J | |
| dc.date.accessioned | 2017-05-05T19:03:05Z | |
| dc.date.available | 2017-05-05T19:03:05Z | |
| dc.date.copyright | 2003 | en_US |
| dc.date.issued | 2017-05-05 | |
| dc.degree.department | Department of Chemistry | |
| dc.degree.level | Doctor of Philosophy Ph.D. | en_US |
| dc.description.abstract | Part A. Vibronic transitions of rhodium monoxide (Rh¹⁶O and Rh¹⁸O) were observed in the 380 to 700 nm region. Laser-induced fluorescence identified two ²[pi]r - X⁴Σ⁻ progressions with origins at {15 667, 15 976} and {15 874, 16 167} cm⁻¹. These progressions were labeled [15.8] ²[pi] - X⁴Σ⁻ and [16.0] ²[pi] - X⁴Σ⁻, respectively. Vibrational parameters were determined for the ground and excited states... Part B. Density functional and configuration interaction calculations on the lowest singlet and triplet potential energy surfaces of hydrogen, fluorine, and chlorine azide for the reactions XN₃ (~X¹A¹) -- NX(X³Σ; a¹Δ) + N₂ (X¹Σ⁺g) and XN₃ -- X(X²S; X²P₃/₂) + N₃(X²[pi]g) (X = H, F, Cl) show that the lowest energy dissociation pathway proceeds exothermically to NX(a) + N₂ . This surface is crossed on the bound singlet region by a dissociative triplet surface. Unimolecular decomposition rates for each pathway and the branching ratio support the experimental observations: HN₃ dissociates to ground state products while FN₃ and CIN₃ produce significant amounts of electronically excited NX. | en_US |
| dc.description.scholarlevel | Graduate | en_US |
| dc.identifier.uri | http://hdl.handle.net/1828/8071 | |
| dc.language | English | eng |
| dc.language.iso | en | en_US |
| dc.rights | Available to the World Wide Web | en_US |
| dc.subject | Molecular dynamics | en_US |
| dc.subject | Chemistry, Physical and theoretical | en_US |
| dc.title | Intramolecular interactions in rhodium monoxide and halogen azides | en_US |
| dc.type | Thesis | en_US |