Plasmonic enhancement of the two photon absorption cross section of an organic chromophore using polyelectrolyte-coated gold nanorods

The effect of plasmonic enhancement on the two-photon absorption cross section of organic chromophores attached to polyelectrolyte-coated gold nanorods was investigated. The magnitudes of such enhancements were confirmed using single and two photon excitations of the chromophore molecules bound to polyelectrolyte-coated gold nanorods. By synthesizing two-, four-, six-, and eight-polyelectrolyte layer coated nanorods of a particular aspect ratio, the distance dependence of the evanescent electromagnetic field on molecular two-photon absorption was observed. Enhancements of 40-fold were observed for the chromophores nearest to the surface.     

Effect of electrostatics techniques on the estimation of thermal conductivity via equilibrium molecular dynamics simulation: application to methane hydrate

Equilibrium molecular dynamics (MD) simulations for three system sizes of fully occupied methane hydrate have been performed at around 265 K to estimate the thermal conductivity using the Ewald, Lekner, reaction field, shifted-force and undamped Fennell–Gezelter methods. The TIP4P water model was used in conjunction with a fully atomistic methane potential with which it had been parameterized from quantum simulation. The thermal conductivity was evaluated by integration of the heat flux autocorrelation function (ACF) derived from the Green–Kubo formalism; this approach vas validated by estimation of the average phonon mean free path. The thermal conductivities predicted by non-periodic techniques were in reasonable agreement with the experimental results of 0.62 and 0.68 W/m K, although it was found that the estimates by the non-periodic techniques were up to 25% larger than those of Lekner and Ewald estimates, particularly for larger systems. The results for the Lekner method exhibited the least variation with respect to system size. A decomposition of the heat flux vector into its respective contributions revealed the importance of electrostatic interactions, and how different electrostatic treatments affect the contribution to the thermal conductivity.     

Computational study of non-covalent interactions in oxirane…XF complexes (X = H,F, Cl,Br, Li) and their F-/Li-substituted analogues

A computational study found oxirane^…XF (X = H, Cl, Br, F, Li) dimers to be energetically stable, with their interaction energies increasing with the magnitude of the XF dipole moment in the order XF = LiF > BrF ～ HF > ClF > F₂. Their relative stabilities roughly correlate with the amount of charge transferred from the lone pairs on the O atom of oxirane to the antibonding σ* orbital of XF. However, the most strongly bound dimer, oxirane^…LiF, is stabilised by the largest dipole but involves the smallest charge transfer. The variation in the strength of the oxirane^…XF interaction was subsequently investigated by the sequential substitution of the protons on oxirane by either electron-donating Li or electron-withdrawing F atoms.     

SSRL users meeting/SPEARfest

It's not exactly Russian roulette, but scheduling October events outdoors is not risk-free, even in usually sunny California. An overflow crowd or more than 400 registered users, ALS staff, and vendors enjoyed a full indoor program featuring science highlights and work-shops spread over two and a half days from October 18 to October 20, 2004. However, a major storm, heralding the onset of the San Francisco Bay Area rainy season, posed a few weather challenges for the events on the ALS patio.

Users' Executive Committee chair Dennis Lindle (University of Nevada, Las Vegas) started the meeting off with a warm welcome to new Berkeley Lab Director Stephen Chu. Coming from a laser-based science background, Chu confessed he was not yet intimately familiar with the ALS but was already hearing that it is one of the best facilities for users to do great science.     

A local instructional theory for the guided reinvention of the group and isomorphism concepts

In this paper I describe a local instructional theory for supporting the guided reinvention of the group and isomorphism concepts. This instructional theory takes the form of a sequence of key steps as students reinvent these fundamental group theoretic concepts beginning with an investigation of geometric symmetry. I describe these steps and frame them in terms of the theory of Realistic Mathematics Education. Each step of the local instructional theory is illustrated using samples of students’ written work or discussion excerpts.     

Counting minimal semi-Sturmian words

A finite Sturmian   word w$w$ is a balanced word over the binary alphabet {a,b}$\{a,b\}$, that is, for all subwords u$u$ and v$v$ of w$w$ of equal length, |_|u|a−_|v|a|≤1$|{\left|u\right|}_a-{\left|v\right|}_a|\le 1$, where _|u|a${\left|u\right|}_a$ and _|v|a${\left|v\right|}_a$ denote the number of occurrences of the letter a$a$ in u$u$ and v$v$, respectively. There are several other characterizations, some leading to efficient algorithms for testing whether a finite word is Sturmian. These algorithms find important applications in areas such as pattern recognition, image processing, and computer graphics. Recently, Blanchet-Sadri and Lensmire considered finite semi-Sturmian words of minimal length and provided an algorithm for generating all of them using techniques from graph theory. In this paper, we exploit their approach in order to count the number of minimal semi-Sturmian words. We also present some other results that come from applying this graph theoretical framework to subword complexity.     

Ionic liquids in external electric and electromagnetic fields: a molecular dynamics study

The non-thermal effects of external electric and electromagnetic fields in the microwave to far-infrared frequency range and at (r.m.s.) electric field intensities of 10^?3 to 0.25?V/Å_r.m.s. on neat salts of 1,3-dimethyl-imidazolium hexafluorophosphate ([dmim][PF₆]) and 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF₆]) have been investigated by means of non-equilibrium molecular dynamics simulation. Significant alterations in molecular mobility were found vis-à-vis zero-field conditions. Using Green–Kubo and transient time correlation function analysis, the electrical conductivity of these ionic liquids has been estimated. The results indicate that ionic liquids respond most significantly to frequencies much lower than those of smaller polar solvents such as water, although the mechanism of the field response is almost exclusively translational.     

New layered compounds with honeycomb ordering: Li3Ni2BiO6, Li3NiM'BiO6 (M' = Mg, Cu, Zn), and the delafossite Ag3Ni2BiO6

The new layered compound Li(3)Ni(2)BiO(6) has been prepared by a solid-state reaction. It crystallizes in the monoclinic C2/m space group; its lamellar structure is characterized by a honeycomb ordering between Ni(2+) and Bi(5+) within the slabs, while Li(+) ions occupy octahedral sites in the interslab space. Stacking defects weakly alter the XRD pattern. By substitution of half of the nickel ions, the new phases Li(3)NiM'BiO(6) (M' = Mg, Cu, Zn) isostructural with Li(3)Ni(2)BiO(6) have been synthesized under similar conditions. All these compounds demonstrate paramagnetic behavior at high temperature, and Li(3)Ni(2)BiO(6) exhibits an antiferromagnetic ordering at 5.5 K. By topotactic molten salt ionic exchange, the new delafossite compound Ag(3)Ni(2)BiO(6) has been also obtained and characterized.     

Coupling of translational and rotational motion in chiral liquids in electromagnetic and circularly polarised electric fields

Non-equilibrium molecular dynamics simulations of R and S enantiomers of 1,1-chlorofluoroethane, both for pure liquids and racemic mixtures, have been performed at 298 K in the absence and presence of both electromagnetic (e/m) and circularly polarised electric (CP) fields of varying frequency (100-2200 GHz) and intensity (0.025-0.2 V ?(-1) (rms)). Significant non-thermal field effects were noted in the coupling of rotational and translational motion; for instance, in microwave and far-infrared (MW/IR) e/m fields, marked increases in rotational and translational diffusion vis-à-vis the zero-field case took place at 0.025-0.1 V ?(-1) (rms), with a reduction in translational diffusion vis-à-vis the zero-field case above 0.1 V ?(-1) (rms) above 100 GHz. This was due to enhanced direct coupling of rotational motion with the more intense e/m field at the ideal intrinsic rotational coupling frequency (approximately 700 GHz) leading to such rapidly oscillating rotational motion that extent of translational motion was effectively reduced. In the case of CP fields, rotational and translational diffusion was also enhanced for all intensities, particularly at approximately 700 GHz. For both MW/IR and CP fields, non-linear field effects were evident above around 0.1 V ?(-1) (rms) intensity, in terms of enhancements in translational and rotational motion. Simulation of 90-10 mol. % liquid mixtures of a Lennard-Jones solvent with R and S enantiomer-solutes in MW/IR and CP fields led to more limited promotion of rotational and translational diffusion, due primarily to increased frictional effects. For both e/m and CP fields, examination of the laboratory- and inertial-frame auto- and cross-correlation functions of velocity and angular velocity demonstrated the development of explicit coupling with the external fields at the applied frequencies, especially so in the more intense fields where nonlinear effects come into play. For racemic mixtures, elements of the laboratory- and inertial-frame velocity and angular velocity were found to couple with each other to a lesser extent.