Preparation of chiral triarylphosphines by Pd-catalysed asymmetric P-C cross-coupling

Enantioselective C-P cross-coupling of diarylphosphines and ortho-substituted aryl iodides has been achieved with >90%ee, using an in situ catalyst prepared from Et,Et-FerroTANE, Pd(2)(dba)(3) x CHCl(3) and LiBr.     

Manganese pentacarbonyl bromide as candidate for a molecular qubit system operated in the infrared regime

Our concept for a quantum computational system is based on qubits encoded in vibrational normal modes of polyatomic molecules. The quantum gates are implemented by shaped femtosecond laser pulses. We adopt this concept to the new species manganese pentacarbonyl bromide [MnBr(CO)5] and show that it is a promising candidate in the mid-infrared (IR) frequency range to connect theory and experiment. As direct reference for the ab initio calculations we evaluated experimentally the absorption bands of MnBr(CO)5 in the mid-IR as well as the related transition dipole moments. The two-dimensional potential-energy surface spanned by the two strongest IR active modes and the dipole vector surfaces are calculated with density-functional theory. The vibrational eigenstates representing the qubit system are determined. Laser pulses are optimized by multitarget optimal control theory to form a set of global quantum gates: NOT, CNOT, Pi, and Hadamard. For all of them simply structured pulses with low pulse energies around 1 microJ could be obtained. Exemplarily for the CNOT gate we investigated the possible transfer to experimental shaping, based on the mask function for pulse shaping in the frequency regime as well as decomposition into a train of subpulses.     

Femtosecond holography in lithium niobate crystals

Spatial gratings are recorded holographically by two femtosecond pump pulses at 388 nm in lithium niobate (LiNbO3) crystals and read out by a Bragg-matched, temporally delayed probe pulse at 776 nm. We claim, to our knowledge, the first holographic pump-probe experiments with subpicosecond temporal resolution for LiNbO3. An instantaneous grating that is due mostly to the Kerr effect as well as a long-lasting grating that results mainly from the absorption caused by photoexcited carriers was observed. The Kerr coefficient of LiNbO3 for our experimental conditions, i.e., pumped and probed at different wavelengths, was approximately 1.0 x 10(-5) cm2/GW.     

Accurate time delay determination for femtosecond X-ray diffraction experiments

Intensity correlations and noise reduction are observed and characterized in the broadband supercontinuum generated by spatio-temporal solitons propagating in air, i.e., in filamentation of ultrashort laser pulses. Large correlations and reduction of the laser noise are observed already at the first steps of the filamentation process, while further propagation results in cascaded χ⁽³⁾ broadening processes and yield complex correlation maps. The spectral range yielding an optimal laser noise reduction of 3.6 dB is found to cover 10 nm around the fundamental wavelength. PACS 42.65.Jx; 42.65.Tg; 42.65.Ky; 42.50.Lc     

Cylindric Versions of Specialised Macdonald Functions and a Deformed Verlinde Algebra

We define cylindric versions of skew Macdonald functions P _λ/μ (q, t) for the special cases q = 0 or t = 0. Fixing two integers n > 2 and k > 0 we shift the skew diagram λ/μ, viewed as a subset of the two-dimensional integer lattice, by the period vector (n, ?k). Imposing a periodicity condition one defines cylindric skew tableaux and associated weight functions. The resulting weighted sums over these cylindric tableaux are symmetric functions. They appear in the coproduct of a commutative Frobenius algebra which is a particular quotient of the spherical Hecke algebra. We realise this Frobenius algebra as a commutative subalgebra in the endomorphisms over a ${U_{q}\widehat{\mathfrak{sl}}(n)}$ Kirillov-Reshetikhin module. Acting with special elements of this subalgebra, which are noncommutative analogues of Macdonald polynomials, on a highest weight vector, one obtains Lusztig’s canonical basis. In the limit q = t = 0, this Frobenius algebra is isomorphic to the ${\widehat{\mathfrak{sl}}(n)}$ Verlinde algebra at level k, i.e. the structure constants become the ${\widehat{\mathfrak{sl}}(n)_{k}}$ Wess-Zumino-Novikov-Witten fusion coefficients. Further motivation comes from exactly solvable lattice models in statistical mechanics: the cylindric Macdonald functions discussed here arise as partition functions of so-called vertex models obtained from solutions to the Yang-Baxter equation. We show this by stating explicit bijections between cylindric tableaux and lattice configurations of non-intersecting paths. Using the algebraic Bethe ansatz the idempotents of the Frobenius algebra are computed.     

Subpicosecond hard x-ray streak camera using single-photon counting

We have developed and characterized a hard x-ray accumulating streak camera that achieves subpicosecond time resolution by using single-photon counting. A high repetition rate of 2 kHz was achieved by use of a readout camera with built-in image processing capabilities. The effects of sweep jitter were removed by using a UV timing reference. The use of single-photon counting allows the camera to reach a high quantum efficiency by not limiting the divergence of the photoelectrons.     

Ultrafast X-ray experiments on structural changes in single crystals of polar molecules

Intramolecular charge transfer in aminobenzonitrile (DIABN) single crystals is studied by a combination of ultrafast techniques. The intramolecular dynamics is probed by time-resolved spectroscopy in the UV/Vis and mid-IR. The intermolecular structural response is investigated by transient X-ray scattering and transmission experiments. A theoretical analysis shows that diffuse scattering and dipole solvation determine the X-ray data. The observed dynamics results from charge transfer reaction leading to strong local changes of molecular dipole moments and related structural rearrangements in the crystal.     

A new impact parameter theory for collision induced lineshifts

A new impact-parameter theory for collision induced line-shifts is described. Comparisons with other theories are discussed. The lineshift oscillation in DCl (0–2) perturbed by HCl is calculated. The effect of velocity averaging is also considered.