Far infrared and millimetre-wave absorption spectra of some low-loss polymers

Absorption spectra in the range 2–50 cm⁻¹ are reported for polyethylene, polypropylene and 'TPX' (basically poly 4-methyl pentene-1). The former has no resonances in this region and the continuum absorption can be represented by a simple quadratic function of wavenumber which, when extrapolated to radio frequencies, gives a good account of the observed losses. Polypropylene and 'TPX' show discrete absorption bands, but for these too there appears to be an underlying continuum. The millimetre-wave absorption possibly arises from a summation of the high frequency wings of the radio region relaxations and the low frequency wings of the far infrared resonances plus an inherent continuum which may be analogous to the broad absorption shown by non-polar liquids in the far infrared.     

Collective properties of polyatomic gases in a magnetic field: Effects on light scattering spectrum

The effect of magnetic fields on collective properties of polyatomic gases has been extended outside the hydrodynamic regime. The calculations are based on a linearized Waldmann-Snider equation. The Waldmann-Snider collision operator is truncated yielding a finite matrix equation. The resulting matrix equation is solved on a computer to yield the polarized and depolarized light scattering spectra. These spectra are calculated in the absence and presence of a magnetic field. For long wavelengths it is found that the magnetic effects are of the same order of magnitude as in the Senftleben-Beenakker effects. For shorter wavelengths the effects disappear due to Doppler effects.This work was supported by NSF GP22881.Alfred P. Sloan Foundation Fellow.NIH Predoctoral Fellow.     

Heterogeneous exciton dynamics revealed by two-dimensional optical spectroscopy

We show that optical two-dimensional (2D) spectroscopy can recover ultrafast heterogeneous dynamics of closely spaced delocalized exciton states from a molecular exciton manifold characterized by a single absorption band. The complete experimental third-order nonlinear optical response from room-temperature J-aggregates in liquid phase is reproduced for the first time with self-consistent Frenkel exciton theory combined with modified Redfield theory. We show that exciton relaxation between the exciton states and nuclear-motion-induced exchange-narrowed energy fluctuations of individual delocalized exciton states can be distinguished because these two processes lead to a distinctively different evolution of the absolute 2D spectrum. Our technique also allows recovery of the variation of the exciton relaxation rates as well as the degree of exciton delocalization across the absorption band.     

Alkenenitriles: Zn-Cu promoted conjugate additions of alkyl iodides in water

[reaction: see text] A new silica-supported zinc-copper matrix dramatically promotes conjugate additions of alkyl iodides to alkenenitriles in water. Acyclic and cyclic nitriles react with functionalized alkyl iodides, overcoming the previous difficulty of performing conjugate additions to disubstituted alkenenitriles with nonstabilized carbon nucleophiles. Conjugate additions with omega-chloroalkyl iodides generate cyclic nitriles primed for cyclization, collectively providing one of the few annulation methods for cyclic alkenenitriles.     

3-Hydroxypyrrolidines from epoxysulfonamides and dimethylsulfoxonium methylide

N-Tosyl-protected 3-hydroxypyrrolidines are prepared by reaction of dimethylsulfoxonium methylide with readily available epoxysulfonamides.     

Nature of the chemical bond in protonated methane

Protonated methane, CH(5)(+), is a key reactive intermediate in hydrocarbon chemistry and a borderline case for chemical structure theory, being the simplest example of hypercoordinated carbon. Early quantum mechanical calculations predicted that the properties of this species could not be associated with only one structure, because it presents serious limitations of the Born-Oppenheimer approximation. However, ab initio molecular dynamics and diffusion Monte Carlo calculations showed that the most populated structure could be pictured as a CH(3) tripod linked to a H(2) moiety. Despite this controversy, a model for the chemical bonds involved in this ion still lacks. Here we present a modern valence bond model for the electronic structure of CH(5)(+). The chemical bond scheme derived directly from our calculations pictures this ion as H(3)C...H(2)(+). The fluxionality can be seen as the result of a proton transfer between C-H bonds. A new insight on the vibrational bands at approximately 2400 and approximately 2700 cm(-1) is suggested. Our results show that the chemical bond model can be profitably applied to such intriguing systems.     

Surface‐enhanced Raman scattering and density functional theory studies of bis(4‐aminophenyl)sulfone

Raman and surface‐enhanced Raman scattering (SERS) spectra of dapsone by using colloidal silver nanoparticles have been recorded. Density functional theory was used for the optimization of ground state geometries and simulation of the vibrational spectrum of this molecule. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman as well as the SERS normal modes and the corresponding assignments, along with the modeling of the free dapsone and the one in the presence of the colloidal silver nanoparticles, the importance of the sulfone group on the SERS effect in dapsone was inferred. Copyright © 2009 John Wiley & Sons, Ltd.     

Event excess in the MiniBooNE search for ¯νμ→¯νe oscillations

The MiniBooNE experiment at Fermilab reports results from a search for ˉν_{μ}→ˉν_{e} oscillations, using a data sample corresponding to 5.66×102? protons on target. An excess of 20.9±14.0 events is observed in the energy range 475相似文献   

Ultra-thin films and surface alloying of Pd on Cu(1 1 1) investigated by medium energy ion scattering

The structure of Pd films on Cu(1 1 1) and the alloying between the films and the substrate have been investigated by medium energy ion scattering (MEIS) using 100 keV H⁺ ions. Data are presented for the and alignments (nominal one- and three-layer alignments, respectively). It is found that beyond 1 ML the Pd grows in a twinned fcc structure, the incommensurate nature of which increases the visibility of the Cu(1 1 1) substrate to MEIS. Deposition of 0.2 ML of Pd produces a structure in which Pd mostly occupies the top two layers which have interlayer distances d₁₂ = 208 ± 4 pm and d₂₃ = 211 ± 4 pm. Some twinning is also present in this structure. Upon annealing 1.6 ML of Pd to 600 K for 1 min, the copper and palladium interdiffuse leaving around 0.4 ML of visible palladium. Energy plots show that there are several layers with an altered structure present over at least part of the surface. This may be due to large scale interdiffusion or alloy island formation. Incremental annealing to successively higher temperatures shows that the structural transformation begins around 500 K.     

Investigation of the excited state structure of DCM via ultrafast electronic pump/vibrational probe

Time resolved visible pump, infrared probe transient absorption measurements of the solutes 4-dicyanomethylene-2-methyl-6-(p-(dimethylamino)styryl)-4H-pyran (DCM) and its isotopomer DCM-d6 are employed to probe the dynamics of charge transfer state formation in dimethyl sulfoxide (DMSO) and acetonitrile (MeCN). We observe a two stage charge transfer (CT): the first step is an instrument-response-limited charge separation to the dicyanomethylene group, and the second involves a structural evolution of the dimethylamino group. Theoretical calculations and isotopic substitution indicate that the observed vibration is due to the dimethylamino group twisting out of plane, stabilizing the charge separation.