Fine-tuning polyoxometalate non-linear optical chromophores: a molecular electronic “Goldilocks” effect

A new aryl-imido polyoxometalate non-linear optical chromophore (POMophore) with a diphenylamino donor group attains the highest βzzz, 0 value (196 × 10−30 esu by Hyper-Rayleigh Scattering, HRS), and best transparency/non-linearity trade off yet for such materials. Stark spectroscopic and DFT investigation of this compound, plus NMe2 and carbazole analogues, show that its high performance results from a combination of strongly dipolar electronic transitions, and strong electronic communication across the π-system

Organoimido-Polyoxometalate Nonlinear Optical Chromophores: A Structural, Spectroscopic, and Computational Study

Ten organoimido polyoxometalate (POM) based chromophores have been synthesized and studied by hyperRayleigh Scattering (HRS), Stark and Resonance Raman spectroscopies and DFT calculations. HRS β0 values for chromophores with resonance electron donors are significant (up to 139 × 10-30 esu, ca. 5 × that of the DAS+ cation), but systems with no donor, or the –NO2 acceptor show no activity, in some cases despite large DFT-predicted β-values. In active systems with short (phenyl) π-bridges, β0-values comfortably exceed that of the purely organic structural analogue N,N-dimethyl-4-nitroaniline (DMPNA), and intrinsic β-values, β0/N3/2 (N = number of bridge π-electrons) thus appear to break empirical performance limits (β0/N3/2 vs λmax) for planar organic systems. However, β0-values obtained for extended systems with a diphenylacetylene bridge are comparable to or lower than that of their nitro analogue N,N-dimethyl-4-[(4-nitrophenyl)ethynyl]-aniline (DMNPEA). Resonance Raman spectroscopy confirms involvement of the POM in the electronic transitions whether donor groups are present or not, but Stark spectroscopy indicates that in their absence the transitions have little dipolar character (hence NLO inactive), consistent with DFT-calculated frontier orbitals which extend over both POM and organic group. Stark and DFT also suggest that β is enhanced in the short compounds because extension of charge transfer (CT) onto the POM increases excited state dipole moment changes. With extended π-systems this effect does not increase CT distances relative to a –NO2 acceptor, so β0-values do not exceed that of DMNPEA. Overall, our results show that: (i) the organoimido–POM unit is an efficient acceptor for 2nd order NLO, but an ineffective donor; (ii) the nature of electronic transitions in arylimido-POMs is strongly influenced by the substituents of the aryl group; and (iii) organoimido-POMs outperform organic acceptors with short π-bridges, but lose their advantage with extended π-conjugation

Ocena gładkiego filtra wysokiego rzędu przy symulacji wielkowirowej z filtrowaniem jawnym w pełni rozwiniętego turbulentnego przepływu w kanale

Explicit filtering with a smooth shape is one of approaches adopted in large eddy simulations (LES). The present work investigates the application of an explicit high order smooth (HOS) filter for the LES of a fully developed turbulent channel flow. The Crank-Nicolson scheme for time marching and second-order finite-volume schemes for spatial derivatives were implemented in this investigation. Implicit filtering, together with the Smagorinsky sub-grid scale (SGS) model, and explicit filtering, along with a HOS filter were studied in a fully turbulent channel flow. In this study, explicit HOS filtering with an explicit filter width to grid size ratio of 2.0 was in agreement with the available direct numerical simulation (DNS) data. However, the mean velocity profile in the streamwise direction was underestimated, and the turbulence intensity in the streamwise direction improved compared to other directions. Moreover, turbulence stresses were well predicted using the mixed SGS and sub-filter stress (SFS) models and applying the HOS filter as an explicit filter.Jawne filtrowanie typu gładkiego jest jedną z metod stosowanych w symulacjach wielkowirowych (tzw. LES). W pracy opisano zastosowanie filtra wysokiego rzędu o charakterystyce gładkiej (HOS) do symulacji wielkowirowej w pełni rozwiniętego turbulentnego przepływu w kanale. W badaniach wykorzystano metodę Cranka-Nicolsona oraz techniki przyrostów czasowych i objętości skończonych drugiego rzędu do wyznaczania pochodnych zmiennych przestrzennych. Przeanalizowano filtrowanie niejawne łącznie z podsieciowym modelem skalowym Smagorynskiego (SGS) oraz filtrowanie jawne HOS w pełni turbulentnego przepływu w kanale. W badaniach wy- kazano, że filtrowanie jawne za pomocą filtra HOS, którego stosunek długości do rozmiaru siatki wynosił 2, dało zgodne wyniki z dostępnymi rezultatami bezpośrednich symulacji numerycznych (DNS). Nieco niedoszacowany okazał się średni profil prędkości w kierunku wzdłużnym przepływu, natomiast poprawiły się wyniki dotyczące intensywności turbulencji właśnie w tym kierunku w porównaniu do kierunków pozostałych. Zaobserwowano ponadto, że zastosowanie kombinacji SGS z użyciem modeli subfiltrów naprężeń (SFS) oraz HOS jako filtru jawnego pozwoliło na poprawne wyznaczenie wartości naprężeń turbulentnych

The effect of waste low-density polyethylene on the mechanical properties of thin asphalt overlay

In recent years, there has been a huge demand for innovative methods to upcycle waste materials. This study aims to explore and evaluate the effect of using waste low-density polyethylene (w-LDPE), collected from waste plastic bags for domestic purposes, on the mechanical properties of dense Thin Asphalt Overlay (TAO). Waste materials have been deemed appropriate in the development of asphalt pavement mixtures, due to the expected enhancement in mixture properties further to the reduction in cost and saving natural resources. Three dosages of w-LDPE were incorporated with asphalt binder: 2%, 4%, and 6%. Marshall stability and flow test, indirect tensile strength, creep compliance, skid resistance, wheel track, Cantabro abrasion loss and tensile strength ratio tests were carried out on both control and modified asphalt mixes to achieve the aim of the study. The results show a substantial enhancement in the performance of TAO modified with w-LDPE when compared to the control mix. The pre-eminent improvement was obtained in the creep compliance test, in which the creep compliance value decreased by 83% compared to the control mixture when using 6% of w-LDPE. This study indicated that using waste material is an effective method of asphalt modification that also contributes to promoting environmental sustainability

Protonic defects and water incorporation in Si and Ge-based apatite ionic conductors

Apatite-type oxide-ion conductors have attracted considerable interest as potential fuel cell electrolytes. Atomistic modelling techniques have been used to investigate oxygen interstitial sites, protonic defects and water incorporation in three silicate and three germanate-based apatite-systems, namely La8Ba2(SiO4)(6)O-2, La-9.33(SiO4)(6)O-2, La-9.67(SiO4)(6)O-2.5, La8Ba2(GeO4)(6)O-2, La-9.33(GeO4)(6)O-2, and La-9.67(GeO4)(6)O-2.5. The simulation models reproduce the complex experimental structures for all of these systems. The interstitial defect simulations have examined the lowest energy configuration and confirm this site to be near the Si/GeO4 tetrahedra. The water incorporation calculations identify the O-H protonic site to be along the O-4 oxygen channel as seen in naturally occurring hydroxy-apatites. The results also show more favourable and exothermic water incorporation energies for the germanate based apatites. This is consistent with recent experimental work, which shows that Ge-apatites take up water more readily than the silicate analogues

Organoimido-polyoxometalate nonlinear optical chromophores: A structural, spectroscopic, and computational study

Ten organoimido polyoxometalate (POM) based chromophores have been synthesized and studied by hyperRayleigh Scattering (HRS), Stark and Resonance Raman spectroscopies and DFT calculations. HRS β0 values for chromophores with resonance electron donors are significant (up to 139 × 10-30 esu, ca. 5 × that of the DAS+ cation), but systems with no donor, or the –NO2 acceptor show no activity, in some cases despite large DFT-predicted β-values. In active systems with short (phenyl) π-bridges, β0-values comfortably exceed that of the purely organic structural analogue N,N-dimethyl-4-nitroaniline (DMPNA), and intrinsic β-values, β0/N3/2 (N = number of bridge π-electrons) thus appear to break empirical performance limits (β0/N3/2 vs λmax) for planar organic systems. However, β0-values obtained for extended systems with a diphenylacetylene bridge are comparable to or lower than that of their nitro analogue N,N-dimethyl-4-[(4-nitrophenyl)ethynyl]-aniline (DMNPEA). Resonance Raman spectroscopy confirms involvement of the POM in the electronic transitions whether donor groups are present or not, but Stark spectroscopy indicates that in their absence the transitions have little dipolar character (hence NLO inactive), consistent with DFT-calculated frontier orbitals which extend over both POM and organic group. Stark and DFT also suggest that β is enhanced in the short compounds because extension of charge transfer (CT) onto the POM increases excited state dipole moment changes. With extended π-systems this effect does not increase CT distances relative to a –NO2 acceptor, so β0-values do not exceed that of DMNPEA. Overall, our results show that: (i) the organoimido–POM unit is an efficient acceptor for 2nd order NLO, but an ineffective donor; (ii) the nature of electronic transitions in arylimido-POMs is strongly influenced by the substituents of the aryl group; and (iii) organoimido-POMs outperform organic acceptors with short π-bridges, but lose their advantage with extended π-conjugation