Quantum chemical studies of reactive species in water

In this thesis, quantum chemical methods have been applied to elucidate the thermodynamics and the kinetics of reactions involving reactive species in water. Due to their high reactivity in water, many transient species are difficult to study by experimental means only. Here, quantum chemical models are used to provide a deeper insight into the chemical nature and aqueous behaviors of such species. In the first chapter, I investigate the gas phase electronic structure and the thermodynamics of inorganic chloramines, bromamines, and bromochloramines, collectively termed halamines. The halamines are halogen oxidants that arise from reactions between ammonia and hypohalous acids during water disinfection processes, and these reactive species are implicated in the formation of disinfection byproducts that are harmful to human health. Despite their relevance in both drinking water chemistry and in biochemistry, the stabilities and speciation of these molecules are difficult to investigate by experimental means. To accurately predict the electronic structures and gas phase thermodynamic properties of halamines, I design a computational protocol, TA14, based on the high-quality Weizmann and Feller-Peterson-Dixon composite methods. TA14 combines a systematic sequence of wave function theory calculations, including the evaluations of dynamical and static electron correlation (CCSDTQ), core/valence electron correlation contributions, scalar and spin-orbit relativistic contributions, and VPT2 anharmonic vibrations. Using TA14, I successfully assess the gas phase total atomization energies, free enthalpies of formation, and Gibbs free energies of formation of halamines within uncertainty bounds of 1-3 kJ/mol. Analysis of the energy components contributing to total atomization energies of halamines reveals that N-Cl and N-Br bonds are held together mostly or entirely by electron correlation forces, with small or even negative Hartree Fock contributions. For example, the Hartree Fock component of the total atomization energy is negative for both NBr3 and NBr2Cl, implying that these molecules would be predicted as unstable without accounting for dynamical electron correlation. Reported thermochemical data enable the determination of equilibrium constants for reactions involving halamines, opening possibilities for more quantitative studies of the chemistry of these poorly understood compounds. In the second chapter, I evaluate the aqueous equilibria and speciation of halamines. I combine theoretical benchmark-quality gas phase Gibbs free energies of formation (chapter 2) with the computed Gibbs free energies of solvation, thereby obtaining aqueous phase Gibbs free energies of formation for halamines. The 'half-and-half' solvation approach, based on averaging the estimates of SMD implicit solvent model and the cluster-continuum solvent model, produces an average error of 3.3 kJ/mol in the free energies of solvation for a set of structurally related molecules containing H, N, O, and Cl. Taking into consideration the combined uncertainties of the computed gas free energy of formation values and the computed free energy of solvation values, we assign an uncertainty of 6-7 kJ/mol to the theoretical standard Gibbs free energies of formation in aqueous phase of halamines. Aqueous Gibbs free energies of formation values are key thermodynamic properties for investigating chemical processes involving halamines during drinking water treatment. The newly reported thermodynamic data can be used to determine the stabilities (reaction equilibria) of halamines in water. Based on our estimated uncertainties of 6-7 kJ/mol in the computed aqueous free energy of formation values of halamines, we expect roughly 1 order-of-magnitude uncertainty in the aqueous equilibrium constants for the reactions leading to the production of halamines in water. ...