The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3-13C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O2 pressure appeared to influence only the rate of reaction. Using 1,3-13C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.The rotational spectrum of 2-methylthiazole was recorded using two pulsed molecular jet Fourier transform microwave spectrometers operating in the frequency range of 2-40 GHz. Due to the internal rotation of the methyl group, all rotational transitions were split into A and E symmetry species lines, which were analyzed using the programs XIAM and BELGI-Cs-hyperfine, yielding a methyl torsional barrier of 34.796 75(18) cm-1. This value was compared with that found in other monomethyl substituted aromatic five-membered rings. The 14N quadrupole coupling constants were accurately determined to be χaa = 0.5166(20) MHz, χbb – χcc = -5.2968(50) MHz, and χab = -2.297(10) MHz by fitting 531 hyperfine components. The experimental results were supplemented by quantum chemical calculations.A theoretical framework for understanding molecular structures is crucial for the development of new technologies such as catalysts or solar cells. Apart from electronic excitation energies, however, only spectroscopic properties of molecules consisting of lighter elements can be computationally described at a high level of theory today since heavy elements require a relativistic framework, and thus far, most methods have only been derived in a non-relativistic framework. Important new technologies such as those mentioned above require molecules that contain heavier elements, and hence, there is a great need for the development of relativistic computational methods at a higher level of accuracy. Here, the Second-Order-Polarization-Propagator-Approximation (SOPPA), which has proven to be very successful in the non-relativistic case, is adapted to a relativistic framework. The equations for SOPPA are presented in their most general form, i.e., in a non-canonical spin-orbital basis, which can be reduced to the canonical case, and the expressions needed for a relativistic four-component SOPPA are obtained. The equations are one-index transformed, giving more compact expressions that correspond to those already available for the four-component RPA. The equations are ready for implementation in a four-component quantum chemistry program, which will allow both linear response properties and excitation energies to be calculated relativistically at the SOPPA level.Preparation of supported metal nanoparticles for catalytic applications often relies on an assumption that the initially prepared wet-impregnated support material is covered with approximately a monolayer of adsorbed species that are shaped into the target nanoparticulate material with a desired size distribution by utilizing appropriate post-treatments that often include calcination and reduction schemes. Here, the formation and evolution of surface nanoparticles were investigated for wet-chemistry deposition of platinum from trimethyl(methylcyclopentadienyl)platinum (IV) precursor onto flat silica supports to interrogate the factors influencing the initial stages of nanoparticle formation. The deposition was performed on silicon-based substrates, including hydroxylated silica (SiO2) and boron-impregnated hydroxylated silica (B/SiO2) surfaces. The deposition resulted in the immediate formation of Pt-containing nanoparticles, as confirmed by atomic force microscopy and x-ray photoelectron spectroscopy. The prepared substrates were later reduced at 550 °C under H2 gas environment. This reduction procedure resulted in the formation of metallic Pt particles. The reactivity of the precursor and dispersion of Pt nanoparticles on the OH-terminated silica surface were compared to those on the B-impregnated surface. The size distribution of the resulting nanoparticles as a function of surface preparation was evaluated, and density functional theory calculations were used to explain the differences between the two types of surfaces investigated.In the framework of thermodynamic perturbation theory (TPT), a new perturbed-chain equation of state (EOS) is presented for a fully flexible Lennard-Jones (LJ) chain system. The EOS is the sum of repulsive and perturbation contributions. The reference term of the EOS is derived based on first- and second-order TPT of Wertheim for the chains interacting with each other through the Weeks-Chandler-Anderson potential model. In order to derive the perturbation term, we have used the radial distribution function of the hard-chain system with a chain range of m = 2-10 and packing fraction range of η = 0.10-0.72, which cover the entire density range from vapor to solid phases. The performance of the EOS is tested against simulation data of the compressibility factor, residual internal energy, and phase equilibrium. A close agreement was observed across all cases. The EOS has three pure component parameters and is able to describe the global vapor-liquid-solid phase diagram of the LJ chain.Using configuration interaction ab initio methods, the evolution of the lowest electronic states of singlet and triplet spin multiplicities of HOSO+ along the stretching and bending coordinates of is investigated. Equilibrium geometries, rotational constants, and harmonic vibrational frequencies of the lowest electronic states are calculated, i.e., X1A’, 11A″, 13A’, and 13A″. Selleck POMHEX The global minimum of the 11A″ state is located below the first dissociation limit and its calculated lifetime is predicted to be 0.40 µs, making it suitable for detection by laser-induced fluorescence. According to the potential energy surfaces, HOSO+ should produce SO2 + and H after ultraviolet photon absorption to the 21A’ state. This work opens the door to investigate the branching ratio and the production rates of SO2 +, SO+, and OH from HOSO+. These insights can help understand the SO2 cycle in the earth’s atmosphere and its effect on cooling our planet.