[show abstract][hide abstract] ABSTRACT: We investigated the key step of Pd-N to Pd-O rearrangement from a model catalytic cycle for the activation of carbon dioxide and methane with static quantum chemical calculations and metadynamics simulation. Our calculations show that different bottlenecks appear in the catalytic cycle but that the investigated rearrangement of the Pd-N to Pd-O bounded complex has a barrier ΔG(#)/ΔF(#) of approximately 20 kJ mol⁻¹ and is therefore accessible at ambient reaction conditions.
Angewandte Chemie International Edition 09/2011; 50(37):A40-5. · 13.73 Impact Factor
[show abstract][hide abstract] ABSTRACT: In this review we present the techniques of ab initio molecular dynamics simulation improved to its current stage where the analysis of existing processes and the prediction of further chemical features and real-world processes are feasible. For this reason we describe the relevant developments in ab initio molecular dynamics leading to this stage. Among them, parallel implementations, different basis set functions, density functionals, and van der Waals corrections are reported. The chemical features accessible through AIMD are discussed. These are IR, NMR, as well as EXAFS spectra, sampling methods like metadynamics and others, Wannier functions, dipole moments of molecules in condensed phase, and many other properties. Electrochemical reactions investigated by ab initio molecular dynamics methods in solution, on surfaces as well as complex interfaces, are also presented.
Topics in current chemistry 08/2011; 307:109-53. · 8.46 Impact Factor
[show abstract][hide abstract] ABSTRACT: We carried out ab initio molecular dynamic simulations in order to determine the free energy surfaces of two selected reactions including solvents, namely a rearrangement of a ruthenium oxoester in water and a carbon dioxide addition to a palladium complex in carbon dioxide. For the latter reaction we also investigated the gas phase reaction in order to take solvent effects into account. We used two techniques to reconstruct the free energy surfaces: thermodynamic integration and metadynamics. Furthermore, we gave a reasonable error estimation of the computed free energy surface. We calculated a reaction barrier of ΔF = 59.5 ± 8.5 kJ mol(-1) for the rearrangement of a ruthenium oxoester in water from thermodynamic integration. For the carbon dioxide addition to the palladium complex in carbon dioxide we found a ΔF = 44.9 ± 3.3 kJ mol(-1) from metadynamics simulations with one collective variable. The investigation of the same reactions in the gas phase resulted in ΔF = 24.9 ± 6.7 kJ mol(-1) from thermodynamic integration, in ΔF = 26.7 ± 2.3 kJ mol(-1) from metadynamics simulations with one collective variable, and in ΔF = 27.1 ± 5.9 kJ mol(-1) from metadynamics simulations with two collective variables.
International Journal of Molecular Sciences 01/2011; 12(2):1389-409. · 2.46 Impact Factor