Ultrafast predissociation dynamics of water molecules excited to the electronic C and D states

Two-photon excitation with femtosecond laser pulses in the spectral range 240-250 nm was used to prepare vapor phase H(2)O and D(2)O in the C (1)B(1) and D (1)A(1) states. Both states are predissociated via the B (1)A(1) state, forming excited OH/OD(A (2)Sigma(+)) as well as ground state OH/OD(X (2)Pi). We used ultrashort infrared probe pulses (1.65-2.42 microm) to control the ratio between these excited and ground state fragments originating from the dissociation process. Time resolved detection of the OH/OD(A (2)Sigma(+)) --> OH/OD(X (2)Pi) fluorescence allows us to monitor the dynamics of the predissociation. For the heterogeneous predissociation out of the C(1)B(1) state life times of (0.5 +/- 0.1) ps and (1.2 +/- 0.1) ps were found for H(2)O and D(2)O, respectively. The purely homogeneous character of the predissociation out of the D (1)A(1) state was monitored.     

Atom diffraction reveals the impact of atomic core electrons on atom-surface potentials

We measured ratios of van der Waals potential coefficients (C3) for different atoms (Li, Na, K, and Rb) interacting with the same surface by studying atom diffraction from a nanograting. These measurements are a sensitive test of atomic structure calculations because C3 ratios are strongly influenced by core electrons and only weakly influenced by the permittivity and geometry of the surface. Our measurement uncertainty of 2% in the ratio C(3)(K)/C(3)(Na) is close to the uncertainty of the best theoretical predictions, and some of these predictions are inconsistent with our measurement.     

Uniform asymptotic analysis for waves in an incompressible elastic rod II. Disturbances superimposed on a pre-stressed state

This paper studies the propagation of disturbances superimposedon a pre-stressed incompressible hyperelastic thin rod. Startingfrom the incremental equations given by Haughton and Ogden (1979,J. Mech. Phys. Solids 27, 179-212 and 489-512), we derive athree parameter-dependent one-dimensional rod equation as thegoverning equation. In particular, it is found that one parameterplays a crucial role. Depending on whether it is larger or smallerthan or equal to a critical value, the shear-wave velocity islarger or smaller than or equal to the bar-wave velocity. Inthe case that these two velocities are equal, there exist travelling-wavesolutions of arbitrary form. This implies that for this particularcase the initial disturbance would propagate along the rod withoutdistortion. To see the influence of the pre-stress in detail,we further consider an initial-value problem with an initialsingularity in the shear strain. The solutions are expressedin terms of integrals through the method of Fourier transform.We then conduct an asymptotic analysis for the solutions. Fora material point in a neighbourhood behind the shear-wave front,the phase function of these integrals has a stationary pointat infinity. Here, we use a technique of uniform asymtotic expansionto handle this case. An asymptotic expansion, correct up toorder O(t^-1), for the shear strain, which is uniformly validin a neighbourhood behind the shear-wave front, is derived.For material points in other spatial domains, the method ofstationary point is applicable, and asymptotic expansions (correctup to order O(t^-1)) are obtained. A novelty is that we are ableto deduce precise qualitative information about the waves inthe far field from our analytic results. Wave profiles for twoconcrete examples are also provided.     

A Novel Method for the Demetalation of Tricarbonyliron–Diene Complexes by a Photolytically Induced Ligand Exchange Reaction with Acetonitrile

The photochemical exchange of all three carbonyl ligands with acetonitrile converts tricarbonyliron–diene complexes into the very labile triacetonitrile-iron–diene complexes. These easily demetalate in high yields to the corresponding free ligands on injection of air at −30°C [Eq. (1)]. The novel demetalation procedure is applied to the tricarbonyliron complexes of cyclopentadienones, cyclohexa-1,3-dienes, and buta-1,3-dienes.     

Dirichlet forms for singular one-dimensional operators and on graphs

We treat the time evolution of states on a finite directed graph, with singular diffusion on the edges of the graph and glueing conditions at the vertices. The operator driving the evolution is obtained by the method of quadratic forms on a suitable Hilbert space. Using the Beurling–Deny criteria we describe glueing conditions leading to positive and to submarkovian semigroups, respectively.     

Intermixed terpyridine-functionalized monolayers on gold: nonlinear relationship between terpyridyl density and metal ion coordination properties

Aiming at the functionalization of surfaces with terpyridine anchors for the coordinative deposition of additional layers, mixed self-assembled monolayers (SAMs) were prepared from binary solutions of 12-(2,2':6',2″-terpyridine-4'-yl)dodecane-1-thiol (TDT) and 1-decanethiol (DT). The SAMs and the order of the constituting molecules were analyzed by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and time-of-flight-secondary ion mass spectrometry (ToF-SIMS). The composition of the (TDT/DT)-SAMs and with it the surface density of terpyridyl groups correlates linearly with the relative concentrations of the two compounds in the solution used for depositing them. In marked contrast, the amount of terpyridine-coordinated Pd(II) ions significantly deviates from this trend with an optimum at a 1:3 ratio of TDT/DT. This indicates a major fraction of the terpyridines in TDT-rich SAMs not to be accessible for Pd(II) ion coordination. In agreement, NEXAFS spectroscopy reveals the alkyl backbones in TDT-rich SAMs not to be ordered, while they are preferentially upright oriented in the optimal 1:3-(TDT/DT)-SAMs. We interpret this in terms of terpyridine backfolding in TDT-rich SAMs, while they are located in accessible positions on top of the SAM in the 1:3-(TDT/DT)-SAM. While the alkyl backbones in the 1:3-(TDT/DT)-SAM are ordered, NEXAFS spectroscopy shows the terpyridyl groups not to have a preferential orientation in this SAM and thus retain enough flexibility to adjust to molecules that are deposited on top of the mixed SAM. In conclusion, the novel SAM does not undergo phase separation and consists predominantly of intermixed phases with adjustable surface density of quite flexible terpyridine anchor groups. The terpyridine-Pd(II) anchors are not only available for a future deposition of the next layer, but the metal ions also represent a sensitive probe for the accessibility of the terpyridyl groups.     

Stripe Order and Spin Dynamics in Nickelates

We report zero field μSR experiments on the lanthanum nickelate La_2−x Sr _x NiO_4+δ system with strontium doping level x between 0 and 0.6. In a single crystal with x=0.33 the internal field distribution shows two separated signals reflecting the antiferromagnetic domains and the non magnetic antiphase domain walls in the spin and charge ordered state below 190 K. Below 70 K a broadening of the low field line is observed. A similar behavior is observed in polycrystalline samples with 0.2≤x≤0.5. This revised version was published online in September 2006 with corrections to the Cover Date.