Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.

Exact Phase Retrieval in Principal Shift-Invariant Spaces

We address the problem of phase retrieval from Fourier transform magnitude spectrum for continuous-time signals that lie in a shift-invariant space spanned by integer shifts of a generator kernel. The phase retrieval problem for such signals is formulated as one of reconstructing the combining coefficients in the shift-invariant basis expansion. We develop sufficient conditions on the coefficients and the bases to guarantee exact phase retrieval, by which we mean reconstruction up to a global phase factor. We present a new class of discrete-domain signals that are not necessarily minimum-phase, but allow for exact phase retrieval from their Fourier magnitude spectra. We also establish Hilbert transform relations between log-magnitude and phase spectra for this class of discrete signals. It turns out that the corresponding continuous-domain counterparts need not satisfy a Hilbert transform relation; notwithstanding, the continuous-domain signals can be reconstructed from their Fourier magnitude spectra. We validate the reconstruction guarantees through simulations for some important classes of signals such as bandlimited signals and piecewise-smooth signals. We also present an application of the proposed phase retrieval technique for artifact-free signal reconstruction in frequency-domain optical-coherence tomography (FDOCT).

The convection during NaClO3 crystal growth observed by the phase shift interferometer

An optical diagnostic system consisting of the Mach-Zehnder interferometer with the phase shift device and an image processor has been developed for the study of the kinetics of the crystal growing process. The dissolution and crystallization process of NaClO3 crystal has been investigated. The concentration distributions around a growing and dissolving crystal have been obtained by using phase-shift of four-steps theory for the interpretation of the interferograms. The convection (a plume flow) has been visualized and analyzed in the process of the crystal growth. The experiment demonstrates that the buoyancy convection dominates the growth rate of the crystal growing face on the ground-based experiment.

Dietary vitamin E inhibits the trans 10-18:1 shift in beef backfat

[EN]Forty feedlot steers were fed a barleygrain-based finishing diet typical for western Canada, with two levels of supplementary vitamin E (468 or 1068 IU head_1 d_1) and the effect on backfat trans-18:1 isomeric profile was determined. Feeding 1068 IU vitamin E reduced the total trans-18:1 content in backfat (P<0.01), as well as the percentage of trans 10-18:1 (P<0.001), which are related to an increased risk for cardiovascular diseases. On the other hand, trans 11-18:1 (vaccenic acid) the precursor for cis 9,trans 11- 18:2 (rumenic acid), which have several purported health benefits, increased (P<0.01). Vitamin E could, therefore, be used to decrease trans-18:1 in beef and improve its isomeric profile.

Case study: Creating a culture shift at Blackburn College

Case study on how three projects at Blackburn College are helping students and staff to engage with digital technologies and enhance learning and teaching and the broader student digital experience.

Red-shift conical emission by femtosecond pulses at low input power

Red-shift conical emission (CE) is observed by femtosecond laser pulse propagating in BK7 at a low input power (compared to those input powers for generation of blue-shift CE). With the increasing input power the blue-shift CE begins to appear whereas the red-shift CE ring (902 nm in our experiment) disappears accompanied by the augment of the central white spot size synchronously. The disappearing of red-shift CE in our experiment is explained such that the increase of axial intensity is much higher than that of ring emission and the augment of the central white spot size with the increasing input laser power.

Pondermotive shift of photoelectron spectra in intense laser field

In a recent experimental work on the excess photon detachment (EPD) of H- ions [Phys. Rev. Lett. 87 (2001) 243001] it has been found that the ponderomotive shift of each EPD peak increases with the order of the EPD channel. By using a nonperturbative quantum scattering theory, we obtain the kinetic energy spectra for the differential detachment rate along the laser polarization for several laser intensities. It is demonstrated that higher order EPD peaks are produced mainly at relatively higher laser intensities. By calculating the overall EPD spectra with varying laser intensities, it is found that the ponderomotive shift of each EPD peak increases with the order of the EPD channel. Our calculations are in good agreement with the experimental observation. It is found that different EPD channels occur mainly when the laser field reaches some values, thus the intensity distribution of the laser field is responsible for the varying ponderomotive shifts.

Red shift and broadening of backward harmonic radiation from electron oscillations driven by femtosecond laser pulse

The characteristics of backward harmonic radiation due to electron oscillations driven by a linearly polarized fs laser pulse are analysed considering a single electron model. The spectral distributions of the electron's backward harmonic radiation are investigated in detail for different parameters of the driver laser pulse. Higher order harmonic radiations are possible for a sufficiently intense driving laser pulse. We have shown that for a realistic pulsed photon beam, the spectrum of the radiation is red shifted as well as broadened because of changes in the longitudinal velocity of the electrons during the laser pulse. These effects are more pronounced at higher laser intensities giving rise to higher order harmonics that eventually leads to a continuous spectrum. Numerical simulations have further shown that by increasing the laser pulse width the broadening of the high harmonic radiations can be controlled.