Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Robustness on resource allocation problems

En problemes d'assignació de recursos, normalment s'han de tenir en compte les incerteses que poden provocar canvis en les dades inicials. Aquests canvis dificulten l'aplicabilitat de les planificacions que s'hagin fet inicialment. Aquesta tesi se centra en l'elaboració de tècniques que consideren la incertesa alhora de cercar solucions robustes, és a dir solucions que puguin continuar essent vàlides encara que hi hagi canvis en l'entorn. Particularment, introduïm el concepte de robustesa basat en reparabilitat, on una solució robusta és una que pot ser reparada fàcilment en cas que hi hagi incidències. La nostra aproximació es basa en lògica proposicional, codificant el problema en una fórmula de satisfactibilitat Booleana, i aplicant tècniques de reformulació per a la generació de solucions robustes. També presentem un mecanisme per a incorporar flexibilitat a les solucions robustes, de manera que es pugui establir fàcilment el grau desitjat entre robustesa i optimalitat de les solucions.