Human carbonic anhydrase II as a host for piano-stool complexes bearing a sulfonamide anchor

d(6)-piano-stool complexes bearing an arylsulfonamide anchor display sub-micromolar affinity towards human Carbonic Anhydrase II (hCA II). The 1.3 ? resolution X-ray crystal structure of [(η(6)-C(6)Me(6))Ru(bispy 3)Cl](+)? hCA II highlights the nature of the host-guest interactions.     

Optical absorption and excitonic coupling in azobenzenes forming self-assembled monolayers: a study based on density functional theory

Based on the analysis of optical absorption spectra, it has recently been speculated that the excitonic coupling between individual azobenzene-functionalized alkanethiols arranged in a self-assembled monolayer (SAM) on a gold surface could be strong enough to hinder collective trans-cis isomerization-on top of steric hindrance [Gahl et al., J. Am. Chem. Soc., 2010, 132, 1831]. Using models of SAMs of increasing complexity (dimer, linear N-mers, and two-dimensionally arranged N-mers) and density functional theory on the (TD-) B3LYP/6-31G* level, we determine optical absorption spectra, the nature and magnitude of excitonic couplings, and the corresponding spectral shifts. It is found that at inter-monomer distances of about 20 ? and above, TD-B3LYP excitation frequencies (and signal intensities) can be well described by the frequently used point-dipole approximation. Further, calculated blue shifts in optical absorption spectra account for the experimental observations made for azobenzene/gold SAMs, and hint to the fact that they can indeed be responsible for reduced switching probability in densely packed self-assembled structures.     

On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4]2- in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)

The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C(4)Py](2)[CuCl(4)] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl(4)](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl(4)](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.     

Explicitly time-dependent coupled cluster singles doubles calculations of laser-driven many-electron dynamics

We report explicitly time-dependent coupled cluster singles doubles (TD-CCSD) calculations, which simulate the laser-driven correlated many-electron dynamics in molecular systems. Small molecules, i.e., HF, H(2)O, NH(3), and CH(4), are treated mostly with polarized valence double zeta basis sets. We determine the coupled cluster ground states by imaginary time propagation for these molecules. Excited state energies are obtained from the Fourier transform of the time-dependent dipole moment after an ultrashort, broadband laser excitation. The time-dependent expectation values are calculated from the complex cluster amplitudes using the corresponding configuration interaction singles doubles wave functions. Also resonant laser excitations of these excited states are simulated, in order to explore the limits for the numerical stability of our current TD-CCSD implementation, which uses time-independent molecular orbitals to form excited configurations.     

Dissipative many-electron dynamics of ionizing systems

In this paper, we perform many-electron dynamics using the time-dependent configuration-interaction method in its reduced density matrix formulation (ρ-TDCI). Dissipation is treated implicitly using the Lindblad formalism. To include the effect of ionization on the state-resolved dynamics, we extend a recently introduced heuristic model for ionizing states to the ρ-TDCI method, which leads to a reduced density matrix evolution that is not norm-preserving. We apply the new method to the laser-driven excitation of H(2) in a strongly dissipative environment, for which the state-resolve lifetimes are tuned to a few femtoseconds, typical for dynamics of adsorbate at metallic surfaces. Further testing is made on the laser-induced intramolecular charge transfer in a quinone derivative as a model for a molecular switch. A modified scheme to treat ionizing states is proposed to reduce the computational burden associated with the density matrix propagation, and it is thoroughly tested and compared to the results obtained with the former model. The new approach scales favorably (～N(2)) with the number of configurations N used to represent the reduced density matrix in the ρ-TDCI method, as compared to a N(3) scaling for the model in its original form.     

Cyclization reactions of 3,4-diazaheptatrienyl metal compounds. Pyridines from an anionic analogue of the Fischer indole synthesis: experiment and theory

Unsymmetrical N,N'-bisalkylidene hydrazines 7a,b, 10a-c and 13, which are accessible in good to excellent yields from hydrazones 6, 9, and 12 and commercially available α,β-unsaturated carbonyl compounds, are converted into 3,4-diazaheptatrienyl anions 14a,b, 16a-c, and 18 by treatment with KO-t-Bu as base. These anionic species form pyridines 15a,b, 5,6-dihydrobenzo[h]quinolones 17a-c, and bipyridine 19 in moderate yields. We interpret thermodynamics and kinetics of these reactions by quantum chemical calculations and discuss this multistep anionic rearrangement, based on an electrocyclic ring formation with a Mo?bius aromatic transition structure 22, the N-N bond fission (25), and the 6-exo-trig cyclization (27) as key steps, considering the results of NICS and NBO-charge calculations. This novel anionic reaction sequence bears an interesting analogy to the mechanism of the (cationic) Fischer indole synthesis. Precursor 10c and product 16c could be characterized by X-ray diffraction.     

Extrinsic homogeneity of parallel submanifolds II

We discuss the question whether a (complete) parallel submanifold M of a Riemannian symmetric space N is an (extrinsically) homogeneous submanifold, i.e. whether there exists a subgroup of the isometries of N which acts transitively on M. In a previous paper, we have discussed this question in case the universal covering space of M is irreducible. It is the subject of this paper to generalize this result to the case when the universal covering space of M has no Euclidian factor.     

Extreme point and halving edge search in abstract order types

Many properties of finite point sets only depend on the relative position of the points, e.g., on the order type of the set. However, many fundamental algorithms in computational geometry rely on coordinate representations. This includes the straightforward algorithms for finding a halving line for a given planar point set, as well as finding a point on the convex hull, both in linear time. In his monograph Axioms and Hulls, Knuth asks whether these problems can be solved in linear time in a more abstract setting, given only the orientation of each point triple, i.e., the set?s chirotope, as a source of information. We answer this question in the affirmative. More precisely, we can find a halving line through any given point, as well as the vertices of the convex hull edges that are intersected by the supporting line of any two given points of the set in linear time. We first give a proof for sets realizable in the Euclidean plane and then extend the result to non-realizable abstract order types.     

Exploiting Sparsity for Semi-Algebraic Set Volume Computation

Foundations of Computational Mathematics - We provide a systematic deterministic numerical scheme to approximate the volume (i.e., the Lebesgue measure) of a basic semi-algebraic set whose...