Browsing by Subject "LUMINESCENCE"

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  • Celaya, Christian A.; Orozco-Ic, Mesias; Dimitrova, Maria; Wirz, Lukas N.; Sundholm, Dage (2020)
    We propose a novel class of gold-containing molecules, which have been designed using conjugated carbon structures as templates. The sp-hybridized carbons of C-2 moieties are replaced with a gold atom and one of the adjacent carbons is replaced by nitrogen. Applying the procedure to hexadehydro[12]annulene yields the well-known cyclic trinuclear gold(i) carbeniate complex. Planar, tubular and cage-shaped complexes can be obtained by taking similar sp-hybridized carbon structures as the starting point.
  • Sabater, Neus; Vicent, Jorge; Alonso, Luis; Verrelst, Jochem; Middleton, Elizabeth M.; Porcar-Castell, Albert; Moreno, José (2018)
    Estimates of Sun-Induced vegetation chlorophyll Fluorescence (SIF) using remote sensing techniques are commonly determined by exploiting solar and/or telluric absorption features. When SIF is retrieved in the strong oxygen (O) absorption features, atmospheric effects must always be compensated. Whereas correction of atmospheric effects is a standard airborne or satellite data processing step, there is no consensus regarding whether it is required for SIF proximal-sensing measurements nor what is the best strategy to be followed. Thus, by using simulated data, this work provides a comprehensive analysis about how atmospheric effects impact SIF estimations on proximal sensing, regarding: (1) the sensor height above the vegetated canopy; (2) the SIF retrieval technique used, e.g., Fraunhofer Line Discriminator (FLD) family or Spectral Fitting Methods (SFM); and (3) the instrument's spectral resolution. We demonstrate that for proximal-sensing scenarios compensating for atmospheric effects by simply introducing the O transmittance function into the FLD or SFM formulations improves SIF estimations. However, these simplistic corrections still lead to inaccurate SIF estimations due to the multiplication of spectrally convolved atmospheric transfer functions with absorption features. Consequently, a more rigorous oxygen compensation strategy is proposed and assessed by following a classic airborne atmospheric correction scheme adapted to proximal sensing. This approach allows compensating for the O absorption effects and, at the same time, convolving the high spectral resolution data according to the corresponding Instrumental Spectral Response Function (ISRF) through the use of an atmospheric radiative transfer model. Finally, due to the key role of O absorption on the evaluated proximal-sensing SIF retrieval strategies, its dependency on surface pressure (p) and air temperature (T) was also assessed. As an example, we combined simulated spectral data with p and T measurements obtained for a one-year period in the Hyytiala Forestry Field Station in Finland. Of importance hereby is that seasonal dynamics in terms of T and p, if not appropriately considered as part of the retrieval strategy, can result in erroneous SIF seasonal trends that mimic those of known dynamics for temperature-dependent physiological responses of vegetation.
  • Kerst, Thomas; Toivonen, Juha (2019)
    Remote detection of alpha radiation is commonly realised by collecting the light, the radioluminescence, that is produced when alpha particles are stopped in air. Radioluminescence of nitric oxide (NO) is primarily emitted between 200 nm and 300 nm, which makes it possible to use it for remote detection under daylight conditions. Quenching by ambient oxygen and water vapour, however, makes it generally difficult to effectively create NO radioluminescence. We present the detection of intense NO radioluminescence in ambient air under standard indoor lighting conditions using a nitrogen purge. The nitrogen contained NO impurities that were intrinsic to the gas and had not explicitly been added. We study the mechanisms that govern the NO radioluminescence production and introduce a model to describe the dynamics of the process. The level of NO contained in the gas was found to determine how successful a purge can be. We conclude by discussing possible applications of the technique in nitrogen-flushed gloveboxes at nuclear facilities where NO concentration of 100 ppb-1ppm would be sufficient for efficient optical alpha radiation detection in standard lighting conditions.
  • Rabaa, Hassan; Omary, Mohammad A.; Taubert, Stefan; Sundholm, Dage (2018)
    The molecular structure of stacked cyclic trinuclear gold(I) complexes [Au-3(RN=CR'(3)](n), with n = 1-4, where R = H, methyl (Me), cyclopentyl ((c)Pe), and phenyl (Ph) and R' = OH and methoxy (OMe) were studied computationally at the second-order Moller-Plesset (MP2) and density functional theory (DFT) levels of theory. At the DFT level, the aurophilic and dispersion interactions were accounted for by using the TPSS functional in combination with the semiempirical D3 correction. The structure optimizations yielded the lowest energy for a slided stacked structure of the [Au-3(HN=COH)(3)](2) dimer, where monomers are slightly shifted relative to one another. At the MP2 level, the slided structure is 32 kJ/mol more stable than the staggered dimer structure, which in turn is energetically 11 kJ/mol below the eclipsed structure. The calculations show that aromatic ligands lead to a planar and prismatic structure of [Au-3(PhN=COMe)(3)](4), whereas for [Au-3('PeN=COMe)(3)](4), a chair conformation is obtained due to steric effects. Excitation energies were calculated for [Au-3(RN=CR')(3)] and [Au-3(RN=CR'(3)](2) with R = H, Me, and 'Pe and R' = OH and OMe at the time-dependent DFT level using the optimized molecular structures of the singlet ground state. To simulate the luminescence spectra, the lowest triplet excitation energy was also calculated for the molecular structure of the lowest triplet state. The calculated excitation energies of [Au-3(HN=COH)(3)] and [Au-3(HN=COH)(3)](2) are compared with values obtained at the approximate singles and doubles coupled cluster (CC2) and the second-order algebraic diagrammatic construction (ADC(2)) levels of theory. The calculated absorption and emission energies reproduce the experimental trends, with extremely large Stokes shifts. A solvoluminescence mechanism is also proposed.
  • Lopez-de-Luzuriaga, Jose M.; Monge, Miguel; Elena Olmos, M.; Rodriguez-Castillo, Maria; Soldevilla, Ines; Sundholm, Dage; Valiev, Rashid R. (2020)
    We report the synthesis of novel perhalophenyl three- coordinated gold( I) complexes using 1,2- bis-(diphenylphosphino)benzene (dppBz) as the chelating ligand and [AuR(tht)] (R = C6F5, C6Cl2F3, C6Cl5) as the perhalophenyl-gold(I) source, leading to [AuR(dppBz)] (R = C6F5 (1), C6Cl2F3 (2), C6Cl5 (3)) complexes. The solid-state structures of compounds 2 and 3 consist of discrete three-coordinated Au(I) complexes, which show a distorted trigonal planar geometry for the gold center with dissimilar Au-P distances. The distorted structural arrangement is closely related to its photophysical properties. The studied complexes display very intense emissions at room temperature (RT) and at 77 K in the solid state. Studies of the emissive properties of the complexes at different temperatures suggest that the emissions are phosphorescent at 77 K and exhibit thermally activated delayed fluorescence (TADF) at RT. First-principle calculations of the photophysical processes yielded rate constants for intersystem crossing and reverse intersystem crossing that are in excellent agreement with experimental data.
  • Greiner, Jonas; Valiev, Rashid R.; Sundholm, Dage (2020)
    Rate constants for radiative and non-radiative transitions of the [Au(HN & xe001;COH)](3) complex and its dimer were calculated within the Herzberg-Teller approximation based on quantum mechanical principles. A high triplet quantum yield was estimated for the monomer. Internal conversion (IC) was found to be the major competing process to the intersystem crossing (ISC) from the lowest excited singlet state (S-1) to the lowest triplet state (T-1). ISC and IC from the spin-mixed T & x303;(1) state also dominate the triplet relaxation process resulting in a negligible phosphorescence quantum yield for the monomer. The IC and ISC rate constants of the dimer are considerably smaller due to much lower Franck-Condon factors. For the dimer a triplet quantum yield of 0.71 was estimated using the extended multi-configuration quasi-degenerate second-order perturbation theory (XMCQDPT2) method to calculate the transition energies. Fluorescence is the major competing process to the ISC relaxation of the S-1 state of the dimer. The ISC and IC processes are insignificant for the relaxation of the T-1 state, resulting in unity phosphorescence quantum yield. The high triplet and phosphorescence quantum yields of the [Au(HN & xe001;COH)](3) dimer make it and its higher oligomers potential candidates as dopants for phosphorescent organic light emitting diodes and as down-converters in solid-state lighting systems.
  • Sundholm, Dage; Rabaa, Hassan; Chiheb, Mohammed; Balch, Alan L. (2019)
    Calculations have been performed at the MP2 and DFT levels for investigating the reasons for the difficulties in synthesizing bis(isocyanide)gold(I) halide complexes. Three-coordinated gold(I) complexes of the type (R3P)(2)(AuX)-X-I (1) can be synthesized, whereas the analogous isocyanide complexes (RNC)(2)(AuX)-X-I (2) are not experimentally known. The molecular structures of (R3P)(2)(AuX)-X-I (X = Cl, Br, and I) and (RNC)(2)(AuX)-X-I with X = halide, cyanide, nitrite, methylthiolate, and thiocyanate are compared and structural differences are discussed. Calculations of molecular properties elucidate which factors determine the strength of the gold-ligand interactions in (RNC)(2)(AuX)-X-I. The linear bonding mode of RNC favors a T-shaped geometry instead of the planar Y-shaped trigonal structure of (R3P)(2)(AuX)-X-I complexes that have been synthesized. An increased polarity of the Au-X bond in 2 leads to destabilization of the Y-shaped structure. Chalcogen-containing ligands or cyanide appear to be good X-ligand candidates for synthesis of (RNC)(2)(AuX)-X-I complexes.
  • Chandra, Sourov; Masuda, Yoshitake; Shirahata, Naoto; Winnik, Francoise M. (2017)
    Impurity-doping in nanocrystals significantly affects their electronic properties and diversifies their applications. Herein, we report the synthesis of transition metal (Mn, Ni, Co, Cu)-doped oleophilic silicon nanocrystals (SiNCs) through hydrolysis/polymerization of triethoxysilane with acidic aqueous metal salt solutions, followed by thermal disproportionation of the resulting gel into a doped-Si/SiO2 composite that, upon HF etching and hydrosilylation with 1-n-octadecene, produces free-standing octadecyl-capped doped SiNCs (diameter approximate to 3 to 8 nm; dopant <0.2 atom %). Metal-doping triggers a red-shift of the SiNC photoluminescence (PL) of up to 270 nm, while maintaining high PL quantum yield (26% for Co doping).
  • Åberg, Annika; Kultti, Seija; Kaakinen, Anu; Eskola, Kari; Salonen, Veli-Pekka (2020)
    Three different till units separated by interstadial fluvial deposits were observed in the Sodankyla area in the River Kitinen valley, northern Finland. The interbedded glaciofluvial sediments and palaeosol were dated by OSL to the Early (79 +/- 12 to 67 +/- 13 ka) and Middle (41 +/- 9 ka) Weichselian. A LiDAR DEM, glacial lineations, the flow direction of till fabrics, esker chains and striations were applied to investigate the glacial flow patterns of the Sodankyla, Kittila and Salla areas. The analysis revealed that the youngest movement of the Scandinavian Ice Sheet is not visible as DEM lineations within the studied areas. The modern morphology in Kittila and Salla shows streamlined landforms of various dimensions mainly oriented from the NW and NNW, respectively, corresponding to the Early/Middle Weichselian ice-flow directions inferred from till fabrics. The Late Weichselian ice flow has produced an insignificant imprint on the landforms. This study suggests a northern location for the ice-divide zone during the Early/Middle Weichselian, and a more western-southwestern position during the Late Weichselian. The OSL ages of 14 +/- 3.3 ka from the aeolian deposits may indicate ice-free areas during the Bolling-Allerod warm period in the vicinity of the River Kitinen.