Tridentate ionic hydrogen-bonding interactions of the 5-fluorocytosine cationic dimer and other 5-fluorocytosine analogues characterized by IRMPD spectroscopy and electronic structure calculations

Ionic hydrogen-bonding interactions have been found in several clusters formed by 5-fluorocytosine (5-FC). The chloride and trimethylammonium cluster ions, along with the cationic (proton-bound) dimer have been characterized by infrared multiple-photon dissociation (IRMPD) spectroscopy and electronic structure calculations performed at the B2PLYP/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. IRMPD action spectra, in combination with calculated spectra and relative energetics, indicate that it is most probable that predominantly a single isomer exists in each experiment. For the 5-FC-trimethylammonium cluster specifically, the calculated spectrum of the lowest-energy isomer convincingly matches the experimental spectrum. Interestingly, the cationic dimer of 5-FC was found to have a single energetically relevant isomer (Cationic-IV) involving a tridentate ionic hydrogen-bonding interaction. The three sites of intermolecular ionic hydrogen bonds in this isomer interact very efficiently, leading to a significant calculated binding energy of 180 kJ/mol. The magnitude of the calculated binding energy for this species, in combination with the strong correlation between the simulated and IRMPD spectra, suggests that a tridentate-proton-bound dimer was observed predominantly in the experiments. Comparison of the calculated relative Gibbs free energies (298 K) for this species and several of the other isomers considered also supports the likelihood of the dominant protonated dimer existing as Cationic-IV.     

Molecular dynamics calculation of activation volumes

We propose a novel approach toward calculating activation and reaction volumes based on MD simulations of reaction systems. The accuracy of the calculated volumes, verified by the comparison to the experimental data, is suitable for quantitative analysis of the experimental volumes of activations in terms of structural parameters of the corresponding transition states.     

Convergence Analysis of the Implicit Euler-discretization and Sufficient Conditions for Optimal Control Problems Subject to Index-one Differential-algebraic Equations

For optimal control problems subject to index-one differential-algebraic equations in semi-explicit form we discuss second order sufficient conditions in form of a coercivity condition taking into account the two-norm discrepancy. Furthermore we introduce a related Riccati-type and Legendre-Clebsch condition which are sufficient for the validity of the coercivity condition. Using the implicit Euler-discretization we approximate the optimal control problem and analyze the convergence of solutions of the local minimum principle for the discretized optimal control problem by applying the general convergence framework of Stetter, which requires the discretization method to be continuous, consistent, and stable.

     

Eisenuntersuchungen

Ohne Zusammenfassung     

Die Unterscheidung von Harz?l und Mineral?l

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Die Flammpunktsbestimmung der Mineralschmier?le

Ohne Zusammenfassung     

On the geometry of master-slave synchronization

In 1990, Pecora and Carroll reported the observation that one can synchronize the orbits of two identical dynamical systems, which may be chaotic, by feeding state variables of one of them to the other one with no feedback, a phenomenon often called master-slave synchronization. We report here some results on the theory of master-slave synchronization for maps and flows, which are all inspired by a similar geometric and coordinate independent point of view to the one introduced in master-slave synchronization by Tresser, Worfolk, and Bass. Our results are variations on the theme that projection often can compensate for expansion.(c) 2002 American Institute of Physics.