Protonated epoxides feature prominently in organic chemistry as reactive intermediates. Gas-phase calculations studying the structure and ring-opening energetics of protonated ethylene oxide, propylene oxide and 2-methyl-1,2-epoxypropane were performed at the B3LYP and MP2 levels (both with the 6-311++G** basis set). Structural analyses were performed for 10 protonated epoxides using B3LYP, MP2, and CCSD/6-311++G** calculations. Protonated 2-methyl-1,2-epoxypropane was the most problematic species studied, where relative to CCSD, B3LYP consistently overestimates the C2-O bond length. The difficulty for DFT methods in modeling the protonated isobutylene oxide is due to the weakness of this C2-O bond. Protonated epoxides featuring more symmetrical charge distribution and cyclic homologues featuring less ring strain are treated with greater accuracy by B3LYP. Ion-pair separation (IPS) of THF-solvated fluorenyl, diphenylmethyl, and trityl lithium was studied computationally. Minimum-energy equilibrium geometries of explicit mono, bis and tris-solvated contact ion pairs (CIPs) and tetrakis-sovlated solvent separated ion pair (SSIPs) were modeled at B3LYP/6-31G*. Associative transition structures linking the tris-solvated CIPs and tetrakis-solvated SIPs were also located. In vacuum, B3LYP/6-31G* ΔHIPS values are 6-8 kcal/mol less exothermic than the experimentally-determined values in THF solution. Incorporation of secondary solvation in the form of Onsager and PCM single-point calculations showed an increase in exothermicity of IPS. Application of a continuum solvation model (Onsager) during optimization at the B3LYP/6-31G* level of theory produced significant changes in the Cα-Li contact distances in the SSIPs. An increase in of ion pair separation exothermicity was observed upon using both PCM and Onsager solvation models, highlighting the importance of both explicit and implicit solvation in modeling of ion pair separation. / Ph. D.

The vibrational potential energy surfaces in electronic ground and excited states of several ring molecules were investigated using several different spectroscopic methods, including far-infrared (IR), Raman, ultraviolet (UV) absorption, fluorescence excitation (FES), and single vibronic level fluorescence (SVLF) spectroscopies. Based on new information obtained from SVLF and millimeter wave spectra, the far-IR spectra of coumaran were reassigned and the one-dimensional ring-puckering potential energy functions for several vibrational states in the S0 ground state were determined. The barrier was found to be 154 cm-1 and the puckering angles to be ± 25°, in good agreement with the millimeter wave barrier of 152 cm-1 and puckering angles of ± 23°. Moreover, the UV absorption and FES spectra of coumaran allowed the one-dimensional ring-puckering potential energy functions in the S1 excited state to be determined. The puckering barrier is 34 cm-1 for the excited state and the puckering angles are ± 14°. Several calculations with different basis sets have been carried out to better understand the unusual vibrational frequencies of cyclopropenone. It was shown that there is strong interaction between the C=O and symmetric C-C stretching vibrations. These results differ quantitatively from a previous normal coordinate calculation and interpretation. The vapor-phase Raman spectrum of 3,7-dioxabicyclo[3.3.0]oct-1,5-ene was analyzed and compared to the predicted spectrum from DFT calculations. The spectrum further shows it has D2h symmetry, in which the skeletons of both rings are planar. The infrared and Raman spectra of vapor-phase and liquid-phase 1,4-benzodioxan and 1,2,3,4-tetrahydronaphthalene were collected and the complete vibrational assignments for both molecules were made. Theoretical calculations predicted the barriers to planarity to be 4809 cm-1 for 1,2,3,4-tetrahydonaphthalene and 4095 cm-1 for 1,4-benzodioxan. The UV absorption, FES, and SVLF spectra of both molecules were recorded and assigned. Both one and two-dimensional potential energy functions of 1,4-benzodioxan for the ring-twisting and ring-bending vibrations were carried out for the S0 and S1(π,π*) states, and these were consistent with the high barriers calculated for both states. The low-frequency spectra of 1,2,3,4-tetrahydronaphthalene in both S0 and S1(π,π*) states were also analyzed.

The vibrational potential energy surfaces in electronic ground and excited states of several ring molecules were investigated using several different spectroscopic methods, including far-infrared (IR), Raman, ultraviolet (UV) absorption, fluorescence excitation (FES), and single vibronic level fluorescence (SVLF) spectroscopies. Based on new information obtained from SVLF and millimeter wave spectra, the far-IR spectra of coumaran were reassigned and the one-dimensional ring-puckering potential energy functions for several vibrational states in the S0 ground state were determined. The barrier was found to be 154 cm-1 and the puckering angles to be ± 25°, in good agreement with the millimeter wave barrier of 152 cm-1 and puckering angles of ± 23°. Moreover, the UV absorption and FES spectra of coumaran allowed the one-dimensional ring-puckering potential energy functions in the S1 excited state to be determined. The puckering barrier is 34 cm-1 for the excited state and the puckering angles are ± 14°. Several calculations with different basis sets have been carried out to better understand the unusual vibrational frequencies of cyclopropenone. It was shown that there is strong interaction between the C=O and symmetric C-C stretching vibrations. These results differ quantitatively from a previous normal coordinate calculation and interpretation. The vapor-phase Raman spectrum of 3,7-dioxabicyclo[3.3.0]oct-1,5-ene was analyzed and compared to the predicted spectrum from DFT calculations. The spectrum further shows it has D2h symmetry, in which the skeletons of both rings are planar. The infrared and Raman spectra of vapor-phase and liquid-phase 1,4-benzodioxan and 1,2,3,4-tetrahydronaphthalene were collected and the complete vibrational assignments for both molecules were made. Theoretical calculations predicted the barriers to planarity to be 4809 cm-1 for 1,2,3,4-tetrahydonaphthalene and 4095 cm-1 for 1,4-benzodioxan. The UV absorption, FES, and SVLF spectra of both molecules were recorded and assigned. Both one and two-dimensional potential energy functions of 1,4-benzodioxan for the ring-twisting and ring-bending vibrations were carried out for the S0 and S1(π,π*) states, and these were consistent with the high barriers calculated for both states. The low-frequency spectra of 1,2,3,4-tetrahydronaphthalene in both S0 and S1(π,π*) states were also analyzed.

Mechanochemistry, the use of mechanical stress to activate chemical reactions, has emerged as a significant area of interest in recent years. Two theoretical approaches have been developed to simulate mechanochemical processes: COnstrained Geometries Simulate External Force (COGEF) and External Force is Explicitly Included (EFEI). In the COGEF method, mechanical stress is simulated by increasing the distance between atoms in a molecule that serve as pulling points (PPs) at a constant rate. In the EFEI methods, a constant external force (Fext) is applied between PPs, allowing the atoms to move to maintain that force. Both methods have been used in the literature to study the ring opening of cyclobutene under mechanochemical conditions. These studies have shown that applying a force between cis PPs in cyclobutene induces ring opening along the conrotatory pathway in COGEF-based simulations and ring opening along the disrotatory pathway in EFEI-based simulations. The latter is consistent with experiments. The work in this thesis identifies the origin of the differences in the outcomes obtained with these two methods, which may be of interest in the context of researchers selecting methods to simulate mechanochemical processes. The results demonstrate that the origin of the difference in behaviour is related to the manner in which these methods alter the potential energy surface (PES) through the application of a mechanical stress. Specifically, the PES obtained with the COGEF method does not contain a minimum energy pathway (MEP) linking cyclobutene to the disrotatory product, whereas the EFEI surface does contain such a path. The differences in PESs suggest that the EFEI method is more suitable to simulate mechanochemical processes. The EFEI approach was then used to examine how the electronic structure evolves to permit a formally forbidden disrotatory reaction to occur. The circumvention of the Woodward-Hoffmann rules was not due to a change in the electronic structure. Instead, the application of an external force shifts the transition state along the reaction coordinate towards the reactants, lowering the barrier for the reactions. The orbital effects that disfavor movement from reactants to products are rendered secondary to mechanochemical factors. / Thesis (Master, Chemistry) -- Queen's University, 2011-12-14 16:47:24.197

A new intermolecular potential energy surface, rovibrational transition frequencies, and line strengths are computed for OCS-OCS and CO2-CS2. The potentials were made by fitting energies obtained from explicitly correlated coupled-cluster calculations and fit using an interpolating moving least squares method. Rovibrational transition frequencies are also calculated for four isotopologues of the N2O dimer using a previously presented potential energy surface. The rovibrational Schroedinger equation for all three dimers is solved with a symmetry-adapted Lanczos algorithm and an uncoupled product basis set. All four intermolecular coordinates are included in the calculation. On the OCS-OCS potential energy surface, a previously unknown, cross-shaped isomer is found along with polar and non-polar isomers. For CO2-CS2, the previously found cross-shaped minima is found along with a slipped-parallel configuration. The associated wavefunctions and energy levels for each of these isomers is presented. To identify states that have a permanent dipole, both calculations of line strengths and vibrational parent analysis is used. For non polar states of, OCS-OCS, and N2O-N2O isotopologues, and all CO2-CO2 states, only vibrational parent analysis was used. Calculated rotational constants differ from their experimental counterparts by less than 0.001 wavenumbers for OCS-OCS and CO2-CS2, and less than 0.002 wavenumbers for any N2O-N2O isotopologue. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2012-08-23 13:19:45.294

The electric charge distribution of molecules such as H₂ and D₂ is inversion-symmetric so that permanent dipole moments do not exist: such molecules are infrared-inactive. It is therefore interesting that gaseous, liquid, and solid hydrogen and its isotopes actually absorb infrared radiation, for example if gas densities are sufficiently high. The observed absorption arises from electric dipole moments induced by intermolecular interactions. It is of a supermolecular origin, due to binary (or higher-order) molecular complexes that may be transient (i.e., in a collisional encounter) or relatively stable (van-der-Waals molecule). Interaction-induced electric dipoles arise from the same mechanisms that generate the intermolecular forces: exchange forces, dispersion forces, and multipolar induction. Recently the induced dipole and potential energy surfaces of H₂ pairs have been obtained by advanced quantum-chemical calculations. Interaction-induced absorption, more commonly called collision-induced absorption (CIA), by H₂ pairs is an important opacity source in the atmospheres of various types of planets and cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, etc., and therefore of special astronomical interest. The emission spectra of cool white dwarf stars differ significantly from the expected blackbody spectra of their cores, mainly due to collision-induced absorption by collisional complexes of hydrogen and helium in the stellar atmospheres. Before proceeding to the frequencies and temperatures of interest it is good to check the new potential energy surface and induced dipole surface in all possible ways by comparison with existing isotopic laboratory measurements. Furthermore, the new potential energy surface is directly compared with previously available, well established intermolecular potential energy surfaces. The electric charge distributions of deuterium and hydrogen are very similar. The new potential energy and induced dipole surfaces were originally obtained to facilitate the computation of the collision-induced absorption of hydrogen. However, by replacing the rotovibrational wavefunctions of H₂ with those of D₂ the surfaces can also be used to calculate the collision-induced absorption of deuterium pairs, thereby probing them further. At the temperature of 298K existing measurements of the collision-induced absorption of D₂--D₂ gas are compared with our quantum scattering calculations in the D₂ fundamental band (approximately 2,500cm⁻¹ to 4,500cm⁻¹). Furthermore, measurements of the collision-induced absorption of deuterium (D₂) in the D₂ first overtone band (about 5,250cm⁻¹ to 7,250cm⁻¹) at 201K are reported. These measurements are compared with ab initio calculations of the absorption spectra. Close agreement of measured and calculated spectra is seen.

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA’s Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth’s primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan’s atmosphere, the ISM, and cold celestial bodies.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23220号 / 工博第4864号 / 新制||工||1759(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 啓文, 教授 佐藤 徹, 教授 田中 勝久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20369号 / 工博第4306号 / 新制||工||1667(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 中村 裕之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24616号 / 工博第5122号 / 新制||工||1979(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 奥田 浩司, 教授 中村 裕之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM