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Rochus Schmid

Publications and source records attributed to Rochus Schmid.

8 recordsLinked to original sources
PubMed2006

A general and efficient pseudopotential Fourier filtering scheme for real space methods using mask functions.

A scheme for the Fourier filtering of pseudopotentials in real space calculations is proposed, in order to reduce the artifact of positional energy dependence ("egg box" effect). It is based on an improved version of the mask function method poposed by Wang [Phys. Rev. B 64, 201107/1 (2001)]. It is easy to implement, efficient, and accurate. By using atom-centered compensation charges, the local part of the pseudopotential becomes short ranged and can be filtered on the same footing as the nonlocal parts. A major advantage of the approach is that a generic set of parameters can be used for different pseudopotentials. A balanced parameter set is derived and validated. In this context a strategy to monitor the extent of grid dependence is introduced. It is found that, given a sufficiently fine grid spacing is used to represent the atomic valence density, the positional energy dependence can be reduced below 0.1 mhartree for all investigated atoms. On the example of a D(3h) symmetric Si(5) cluster and the C(60) molecule it is demonstrated that the artificial symmetry breaking of both bond lengths and orbital energies can substantially be reduced by the filtering scheme.

Journal Article↗
PubMed2005

Mechanistic insights into an unprecedented C-C bond activation on a Rh/Ga bimetallic complex: a combined experimental/computational approach.

The unusual rearrangement of [RhCp(GaCp)(CH(3))(2)] (1c) to [RhCp(C(5)Me(4)Ga(CH(3))(3))] (2) is presented and its mechanism is discussed in detail. (13)C MAS NMR spectroscopy revealed that the title reaction proceeds cleanly not only in solution but also in solid state, which supports a unimolecular reaction pathway. On the basis of (1)H, (13)C, and ROESY NMR spectroscopy as well as isolation and structural elucidation of the hydrolysis product, the compound [RhCp(endo-eta(4)-C(5)Me(5)GaMe(2))] (3a) was identified as a crucial reaction intermediate. DFT calculations on the B3LYP level of theory support this assignment and suggest a concerted C-C bond activation mechanism that topologically takes place at the gallium center. Furthermore, two fluxional processes of the reaction intermediate 3a were studied experimentally as well as by computational methods. First, a mechanism takes place similar to a ring-slipping process that exchanges a GaMe(2) group between adjacent ring carbon atoms within the same Cp ring. This process proceeds at a rate comparable to the NMR time scale and indeed is calculated to be energetically very favorable. Second, a unimolecular exchange process of the GaMe(2) group between the two Cp rings of 3a could be experimentally proven by the introduction of phenyl substituents as a label into the Cp ligands at both sites, the rhodium as well as the gallium center. A series of experiments including deuteration studies and competition reactions was performed to substantiate the suggested mechanism being in accordance with DFT calculations on possible transition states.

Journal Article↗
PubMed2005

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

Gallium↗
PubMed2004

Car-Parrinello simulations with a real space method.

An approach for Car-Parrinello type molecular dynamics simulations using real space discretized wave functions is presented. The implementation uses a higher order finite difference approximation for the Laplacian in the kinetic energy operator and in the Poisson equation for the evaluation of the Hartree energy. Norm conserving pseudopotentials are employed to replace the nucleus-core interactions. Both nuclei and wave functions are propagated with a second-order Verlet propagator with a timestep comparable to standard plane wave implementations. The orthonormality constraints are fulfilled via Lagrange multipliers. Both periodic and nonperiodic boundary conditions can directly be imposed within the real space approach. In order to maintain energy conservation both forces on the nuclei and the wave functions must be sufficiently accurate. It is shown that the spurious energy dependence on the nuclear positions with respect to the grid points, which is an inevitable artifact of the discretization, is mirrored in the nuclear forces, and does not affect energy conservation. In contrast to the plane wave methodology, the Hartree energy is calculated via an iterative solution of the Poisson equation. As a result, the quality of the forces on the wave function crucially depends on its convergence, as well as on the accuracy of the approximation for the boundary values in nonperiodic calculations. The influence of these factors on the energy conservation is investigated. It is shown that Car-Parrinello simulations can be performed with real space wave functions, given a proper prescription to calculate the Hartree potential is used.

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