Browsing by Subject "SPECTRA"

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  • Bes, René; Leinders, Gregory; Kvashnina, Kristina O. (2022)
    The uranium valence electronic structure in the prototypical undistorted perovskite KUO3 is reported on the basis of a comprehensive experimental study using multi-edge HERFD-XAS and relativistic quantum chemistry calculations based on density functional theory. Very good agreement is obtained between theory and experiments, including the confirmation of previously reported Laporte forbidden f –f transitions and X-ray photoelectron spectroscopic measurements. Many spectral features are clearly identified in the probed U-f, U- p and U-d states and the contribution of the O-p states in those features could be assessed. The octahedral crystal field strength, 10Dq, was found to be 6.6 (1.5) eV and 6.9 (4) eV from experiment and calculations, respectively. Calculated electron binding energies down to U-4f states are also reported.
  • Baryshnikov, G. V.; Valiev, R. R.; Cherepanov, V. N.; Karaush-Karmazin, N. N.; Minaeva, V. A.; Minaev, B. F.; Ågren, H. (2019)
    The electronic structure, absorption and emission spectra, aromaticity and photophysical behavior of the recently synthesized tetrasilatetrathia[8]circulene and tetragermatetrathia[8]circulene compounds have been studied computationally. Both compounds demonstrate a specific bifacial aromaticity, which is unusual for hetero[8]circulenes; the inner eight-membered core sustains an expected strong paratropic magnetically-induced ring current, while the outer perimeter contains saturated Si(Et)2 and Ge(Et)2 moieties which break the conjugation between the thiophene rings. The overall magnetically-induced ring current for both studied circulenes is close to zero because of the strong local diatropic currents in each thiophene ring that compensate the paratropic counterpart. The electronic absorption and emission spectra of tetrasilatetrathia[8]circulene and tetragermatetrathia[8]circulene demonstrate a clear visible vibronic progression. The 0–0 band is the most active one in the absorption spectra, while in the fluorescence spectra the 0–1 band composed of several normal vibrations is more intense compared with the 0–0 band in excellent agreement with experiment. Accounting for spin–orbit coupling effects, an analysis of the photophysical constants for the two compounds demonstrates: (1) a clear manifestation of the internal heavy atom effect on the inter-system crossing efficiency; (2) one to two order domination of non-radiative rates over the fluorescence rate; and (3) that the S1–S0 internal conversion is extremely slow and can not compete with the fluorescence, while the S1–Tn inter-system crossing is a main deactivation channel of the S1 excited state. These results provide new insight into the electronic structure and photophysics of tetrasilatetrathia[8]circulene and tetragermatetrathia[8]circulene as novel standalone representatives of hetero[8]circulenes – tetraannelated derivatives of tetrathienylene.
  • Delhommaye, S.; Radtke, G.; Brouder, Ch; Collins, S. P.; Huotari, Simo; Sahle, Ch; Lazzeri, M.; Paulatto, L.; Cabaret, D. (2021)
    This study aims at assessing the thermal nuclei motion effects on the multipole transition channels involved in two core-level spectroscopies, x-ray absorption spectroscopy (XAS) and x-ray Raman scattering (XRS). Temperature effects on the 1s -> s monopole, 1s -> p dipole, and 1s -> d quadrupole transitions are investigated using two reference systems for which we present original experimental data: alpha-Al2O3 at the Al K edge probed by XRS at room temperature and rutile TiO2 at the Ti K pre-edge probed by XAS at temperatures ranging from 6 to 700 K. Through the latter, this work enlightens the part of the pre-edge peak enhancement due to temperature in the K pre-edge region of 3d transition metal, which is known to be routinely used to determine the concentration, valence or symmetry of the probed element in a given sample. Nuclear thermal fluctuations are taken into account using a method based on density functional theory that consists in averaging spectra over atomic configurations, generated within the harmonic approximation and obeying quantum statistics at finite temperature. Since only a finite number of such configurations are used, the numerically averaged spectra generally lose the symmetry of the equilibrium crystal positions. In this paper, we demonstrate that the physical average has to be symmetric and propose a method to restore the physical angular dependence of the spectra. The approach is successfully applied to investigate the angular dependent XAS spectra in rutile as a function of temperature. The two systems under study allow to draw general conclusions regarding the effect of nuclear quantum fluctuations on the different transition channels available to both core-level spectroscopies.
  • Moreau, Juulia-Gabrielle; Joeleht, Argo; Aruvali, Jaan; Heikkila, Mikko J.; Stojic, Aleksandra N.; Thomberg, Thomas; Plado, Juri; Hietala, Satu (2022)
    Stoichiometric troilite (FeS) is a common phase in differentiated and undifferentiated meteorites. It is the endmember of the iron sulfide system. Troilite is important for investigating shock metamorphism in meteorites and studying spectral properties and space weathering of planetary bodies. Thus, obtaining coarse-grained meteoritic troilite in quantities is beneficial for these fields. The previous synthesis of troilite was achieved by pyrite or pyrrhotite heating treatments or chemical syntheses. However, most of these works lacked a visual characterization of the step by step process and the final product, the production of large quantities, and they were not readily advertised to planetary scientists or the meteoritical research community. Here, we illustrate a two-step heat treatment of pyrite to synthesize troilite. Pyrite powder was decomposed to pyrrhotite at 1023-1073 K for 4-6 h in Ar; the run product was then retrieved and reheated for 1 h at 1498-1598 K in N-2 (gas). The minerals were analyzed with a scanning electron microscope, X-ray diffraction (XRD) at room temperature, and in situ high-temperature XRD. The primary observation of synthesis from pyrrhotite to troilite is the shift of a major diffraction peak from similar to 43.2 degrees 2 theta to similar to 43.8 degrees 2 theta. Troilite spectra matched an XRD analysis of natural meteoritic troilite. Slight contamination of Fe was observed during cooling to troilite, and alumina crucibles locally reacted with troilite. The habitus and size of troilite crystals allowed us to store it as large grains rather than powder; 27 g of pyrite yielded 17 g of stochiometric troilite.
  • Oleynik, Philipp; Vainio, Rami; Punkkinen, Arttu; Dudnik, Oleksiy; Gieseler, Jan; Hedman, Hannu-Pekka; Hietala, Heli; Hæggström, Edward; Niemelä, Petri; Peltonen, Juhani; Praks, Jaan; Punkkinen, Risto; Säntti, Tero; Valtonen, Eino (2020)
    RADMON is a small radiation monitor designed and assembled by students of University of Turku and University of Helsinki. It is flown on-board Aalto-1, a 3-unit CubeSat in low Earth orbit at about 500 km altitude. The detector unit of the instrument consists of two detectors, a Si solid-state detector and a CsI(Tl) scintillator, and utilizes the Delta E-E technique to determine the total energy and species of each particle hitting the detector. We present the results of the on-ground and in-flight calibration campaigns of the instrument, as well as the characterization of its response through extensive simulations within the Geant4 framework. The overall energy calibration margin achieved is about 5%. The full instrument response to protons and electrons is presented and the issue of proton contamination of the electron channels is quantified and discussed. (C) 2019 COSPAR. Published by Elsevier Ltd. All rights reserved.
  • Saarinen, Jukka Kalle Samuel; Gütter, Friederike; Lindman, Mervi M; Agopov, Mikael; Fraser-Miller, Sara J.; Scherließ, Regina; Jokitalo, Eija; Almeida Santos, Helder; Peltonen, Leena; Isomäki, Antti; Strachan, Clare J. (2019)
    A wide variety of nanoparticles are playing an increasingly important role in drug delivery. Label-free imaging techniques are especially desirable to follow the cellular uptake and intracellular fate of nanoparticles. The combined correlative use of different techniques, each with unique advantages, facilitates more detailed investigation about such interactions. The synergistic use of correlative coherent anti-Stokes Raman scattering and electron microscopy (C-CARS-EM) imaging offers label-free, chemically-specific, and (sub)-nanometer spatial resolution for studying nanoparticle uptake into cells as demonstrated in the current study. Coherent anti-Stokes Raman scattering (CARS) microscopy offers chemically-specific (sub)micron spatial resolution imaging without fluorescent labels while transmission electron microscopy (TEM) offers (sub)-nanometer scale spatial resolution and thus visualization of precise nanoparticle localization at the sub-cellular level. This proof-of-concept imaging platform with unlabeled drug nanocrystals and macrophage cells revealed good colocalization between the CARS signal and electron dense nanocrystals in TEM images. The correlative TEM images revealed subcellular localization of nanocrystals inside membrane bound vesicles, showing multivesicular body (MVB)-like morphology typical for late endosomes (LEs), endolysosomes, and phagolysosomes. C-CARS-EM imaging has much potential to study the interactions between a wide range of nanoparticles and cells with high precision and confidence.
  • The CMS collaboration; Sirunyan, A. M.; Eerola, P.; Kirschenmann, H.; Pekkanen, J.; Voutilainen, M.; Havukainen, J.; Heikkilä, J. K.; Järvinen, T.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Laurila, S.; Lehti, S.; Lindén, T.; Luukka, P.; Mäenpää, T.; Siikonen, H.; Tuominen, E.; Tuominiemi, J.; Tuuva, T. (2018)
    The differential yields of charged particles having pseudorapidity within vertical bar eta vertical bar < 1 are measured using xenon-xenon (XeXe) collisions at root S-NN = 5.44 TeV. The data, corresponding to an integrated luminosity of 3.42 mu b(-1), were collected in 2017 by the CMS experiment at the LHC. The yields are reported as functions of collision centrality and transverse momentum, pT, from 0.5 to 100 GeV. A previously reported pT spectrum from proton-proton collisions at root S = 5.02 TeV is used for comparison after correcting for the difference in center-of-mass energy. The nuclear modification factors using this reference, R-AA*, are constructed and compared to previous measurements and theoretical predictions. In head-on collisions, the R-AA* has a value of 0.17 in the pT range of 6-8 GeV, but increases to approximately 0.7 at 100 GeV. Above approximate to 6 GeV, the XeXe data show a notably smaller suppression than previous results for lead-lead (PbPb) collisions at root S-NN = 5.02 TeV when compared at the same centrality (i.e., the same fraction of total cross section). However, the XeXe suppression is slightly greater than that for PbPb in events having a similar number of participating nucleons.
  • Augustyn, Bozena; Stepien, Piotr; Poojari, Chetan; Mobarak, Edouard; Polit, Agnieszka; Wisniewska-Becker, Anna; Rog, Tomasz (2019)
    Nanodiscs are suitable tools for studies of membrane proteins (MPs) due to their ability to mimic native biological membranes, and several MP structures are solved in nanodiscs. Among the various cell membrane components, cholesterol (CHL) is known to regulate protein function and its concentration can reach up to 50 mol %. However, studies comprising cholesterol are challenging due to its hydrophobic nature, hence, nanodiscs with only a low cholesterol concentration have been studied. To overcome the problem, cholesterol analogs with high solubility in polar solutions are often used, and one of them is cholesteryl hemisuccinate (CHS). Nevertheless, in molecular dynamics (MD) simulation, this is not an obstacle. In this study, we performed MD simulations of nanodiscs containing neutral phosphatidylcholine (POPC) lipids, negatively charged phosphatidylglycerol (POPG) lipids, CHL, or negatively charged cholesterol analog, CHS. Our simulations show that CHS increases the order of lipids in nanodiscs; the effect is, however, weaker than CHL and even smaller in nanodiscs. Furthermore, CHS gathered around scaffold proteins while cholesterol was uniformly distributed in the nanodiscs. Thus, nanodiscs with CHS are heterogeneous and not equivalent to nanodiscs with CHL. Finally, we also observed the increased concentration of POPG near the scaffold proteins, driven by electrostatic interactions. The MD results are experimentally validated using electron paramagnetic resonance spectroscopy. These results show that nanodiscs are, in fact, complex structures not easily comparable with planar lipid bilayers.
  • Vegh, Russell B.; Bravaya, Ksenia B.; Bloch, Dmitry A.; Bommarius, Andreas S.; Tolbert, Laren M.; Verkhovsky, Michael; Krylov, Anna I.; Solntsev, Kyril M. (2014)
  • Benatto, L.; Marchiori, C. F. N.; Talka, T.; Aramini, M.; Yamamoto, N. A. D.; Huotari, S.; Roman, L. S.; Koehler, M. (2020)
    The difference in aggregation size of the C-60 and C-70 fullerenes affect the photovoltaic performance of devices assembled in the so-called bilayer architecture with poly [2,7-(9,9- dioctyl- dibenzosilole)- alt-4,7- bis(thiophen-2-yl)benzo- 2,1,3- thiadiazole] (PSiF-DBT) as the electron donor material. Despite the better performance of the C-70 devices, which is related to the high absorption coefficient in the visible range and the superior charge transport properties, the short-circuit current variation upon annealing treatment at 100 degrees C is approximately twice bigger when the C-60 is the acceptor. We attribute this effect to the tendency of C-60 in form smaller aggregate domains relatively to the C-70. The increased roughness on the polymeric surface after annealing results in an enhanced donor/acceptor contact area and assists the fullerene diffusion deeper inside the polymeric layer. This effect leads to a better mixing between donor and acceptor species and create a interpenetrating layer close to the so-called bulk heterojunction. Since C-60 forms smaller aggregates, this mechanism is more pronounced for this molecule. Therefore, a significant variation in the performance of the C-60 devices is observed after this kind of treatment. Density Functional Theory calculations of the potential energy of interaction between two fullerene molecules and X-Ray measurements gives evidences to support this idea. In addition, combining spectrally resolved external quantum efficiency measurements with optical modeling our results also indicate the occurrence of the bilayer interfacial mixing for PSiF-DBT/C-60.
  • Valiev, R. R. (2020)
    The effect of the nonadiabatic electronic state-mixing between the S-1 and S-2 states in tetraoxa[8]circulene is investigated computationally. The calculations show that the nonadiabatic electronic state-mixing effect on the fluorescence of tetraoxa[8]circulene is one million times weaker than the Herzberg-Teller vibronic effect. Analysis of the promotive modes of the S-0 -> S-1 and S-1 -> S-0 transitions shows that they are same for both absorption and emission. Also, the Duschinsky effect is found to be very weak for the S-0 -> S-1 and S-1 -> S-0 transitions. The Jahn-Teller symmetry breaking of the S-2 state leads to an energy splitting of similar to 1500 cm(-1) between the two components of the S-2 state.
  • Guryanov, Ivan; Korzhikov-Vlakh, Viktor; Bhattacharya, Madhushree; Biondi, Barbara; Masiero, Giulia; Formaggio, Fernando; Tennikova, Tatiana; Urtti, Arto (2021)
    The design of efficient vascular endothelial growth factor (VEGF) inhibitors is a high-priority research area aimed at the treatment of pathological angiogenesis. Among other compounds, v114* has been identified as a potent VEGF-binding peptide. In order to improve the affinity to VEGF, we built a conformational constrain in its structure. To this aim, C-alpha-tetrasubstituted amino acid Aib was introduced into the N-terminal tail, peptide loop, or C-terminal helix. NMR studies confirmed the stabilization of the helical conformation in proximity to the Aib residue. We found that the induction of the N-terminal helical structure or stabilization of the C-terminal helix can noticeably increase the peptide affinity to the VEGF. These peptides efficiently inhibited VEGF-stimulated cell proliferation as well. The insertion of the non-proteinogenic Aib residue significantly enhanced the stability of the peptides in the vitreous environment. Thus, these Aib-containing peptides are promising candidates for the design of VEGF inhibitors with improved properties.
  • The CMS collaboration; Sirunyan, A. M.; Eerola, P.; Kirschenmann, H.; Pekkanen, J.; Voutilainen, M.; Havukainen, J.; Heikkilä, J. K.; Järvinen, T.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Laurila, S.; Lehti, S.; Lindén, T.; Luukka, P.; Mäenpää, T.; Siikonen, H.; Tuominen, E.; Tuominiemi, J.; Tuuva, T. (2018)
    The pseudorapidity distributions of dijets as functions of their average transverse momentum (p(T)(ave)) are measured in proton-lead (pPb) and proton-proton (pp) collisions. The data samples were collected by the CMS experiment at the CERN LHC, at a nucleon-nucleon center-of-mass energy of 5.02 TeV. A significant modification of the pPb spectra with respect to the pp spectra is observed in all p(T)(ave) intervals investigated. The ratios of the pPb and pp distributions are compared to next-to-leading order perturbative quantum chromodynamics calculations with unbound nucleon and nuclear parton distribution functions (PDFs). These results give the first evidence that the gluon PDF at large Bjorken x in lead ions is strongly suppressed with respect to the PDF in unbound nucleons.
  • V. Baryshnikov, Glib; Valiev, Rashid; Kuklin, Artem; Sundholm, Dage; Ågren, Hans (2019)
    Cyclo[18]carbon (C18) is studied computationally at density functional theory (DFT) and ab initio levels to obtain insights into its electronic structure, aromaticity, and adsorption properties on the NaCl surface. DFT functionals with a small amount of Hartree-Fock exchange as well as XMC-QDPT2 calculations fail to determine the experimentally observed polyyne molecular structure revealing a cumulene-type geometry. Exchange-correlation functionals with a large amount of Hartree-Fock ex-change as well as ab initio CASSCF calculations yield the polyyne structure is a ground state while the cumulene structure corresponds to the transition state between the two inverted polyyne structures through the Kekule distortion. The polyyne and the cumulene structures are found to be doubly Hückel aromatic. The calculated adsorption energy of cyclo[18]carbon on the NaCl surface is small (37 meV/C) and almost the same for both structures implying that the surface does not stabilize a particular geometry.
  • Hofmann, F.; Sanders, J. S.; Clerc, N.; Nandra, K.; Ridl, J.; Dennerl, K.; Ramos-Ceja, M.; Finoguenov, A.; Reiprich, T. H. (2017)
    Context. The eROSITA mission will provide the largest sample of galaxy clusters detected in X-ray to date (one hundred thousand expected). This sample will be used to constrain cosmological models by measuring cluster masses. An important mass proxy is the electron temperature of the hot plasma detected in X-rays. Aims. We want to understand the detection properties and possible bias in temperatures due to unresolved substructures in the cluster halos. Methods. We simulated a large number of galaxy cluster spectra with known temperature substructures and compared the results from analysing eROSITA simulated observations to earlier results from Chandra. Results. We were able to constrain a bias in cluster temperatures and its impact on cluster masses, as well as cosmological parameters derived from the survey. We found temperatures in the eROSITA survey to be biased low by about five per cent due to unresolved temperature substructures (compared to emission-weighted average temperatures from the Chandra maps). This bias would have a significant impact on the eROSITA cosmology constraints if not accounted for in the calibration. Conclusions. We isolated the bias effect that substructures in galaxy clusters have on temperature measurements and their impact on derived cosmological parameters in the eROSITA cluster survey.
  • Koskelo, Jaakko; Fugallo, Giorgia; Hakala, Mikko; Gatti, Matteo; Sottile, Francesco; Cudazzo, Pierluigi (2017)
    We present a general picture of the exciton properties of layered materials in terms of the excitations of their single-layer building blocks. To this end, we derive a model excitonic Hamiltonian by drawing an analogy with molecular crystals, which are other prototypical van der Waals materials. We employ this simplified model to analyze in detail the excitation spectrum of hexagonal boron nitride (hBN) that we have obtained from the ab initio solution of the many-body Bethe-Salpeter equation as a function of momentum. In this way, we identify the character of the lowest-energy excitons in hBN, discuss the effects of the interlayer hopping and the electron-hole exchange interaction on the exciton dispersion, and illustrate the relation between exciton and plasmon excitations in layered materials.
  • CORE Collaboration; Natoli, P.; Kiiveri, K.; Lindholm, V.; Keihänen, E.; Kurki-Suonio, H.; Väliviita, J. (2018)
    We present an analysis of the main systematic effects that could impact the measurement of CMB polarization with the proposed CORE space mission. We employ timeline to-map simulations to verify that the CORE instrumental set-up and scanning strategy allow us to measure sky polarization to a level of accuracy adequate to the mission science goals. We also show how the CORE observations can be processed to mitigate the level of contamination by potentially worrying systematics, including intensity-to-polarization leakage due to bandpass mismatch, asymmetric main beams, pointing errors and correlated noise. We use analysis techniques that are well validated on data from current missions such as Planck to demonstrate how the residual contamination of the measurements by these effects can be brought to a level low enough not to hamper the scientific capability of the mission, nor significantly increase the overall error budget. We also present a prototype of the CORE photometric calibration pipeline, based on that used for Planck, and discuss its robustness to systematics, showing how CORE can achieve its calibration requirements. While a fine-grained assessment of the impact of systematics requires a level of knowledge of the system that can only be achieved in a future study phase, the analysis presented here strongly suggests that the main areas of concern for the CORE mission can be addressed using existing knowledge, techniques and algorithms.
  • Valiev, R. R.; Cherepanov, V. N.; Baryshnikov, G. V.; Sundholm, D. (2018)
    A method for calculating the rate constants for internal-conversion (k(IC)) and intersystem-crossing (k(ISC)) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k(IC) and k(ISC) for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq(3) and fac-Ir(ppy)(3), which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq(3) and fac-Ir(ppy)(3) agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules.
  • Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C.; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J.; Yliperttula, Marjo (2016)
    In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is possible to overcome the strong fluorescence background that usually interferes with the much weaker Raman spectra. Second, using the high photon energy excitation light source, we are able to generate a stronger Raman signal compared to traditional instruments. In addition, observations in the time domain can be performed, thus enabling new capabilities in the field of Raman and fluorescence spectroscopy. With this system, we demonstrate for the first time the possibility of recording fluorescence-suppressed Raman spectra of solid, amorphous and crystalline, and non-photoluminescent and photoluminescent drugs such as caffeine, ranitidine hydrochloride, and indomethacin (amorphous and crystalline forms). The raw data acquired by utilizing only the picosecond pulsed laser and a CMOS SPAD detector could be used for identifying the compounds directly without any data processing. Moreover, to validate the accuracy of this time-resolved technique, we present density functional theory (DFT) calculations for a widely used gastric acid inhibitor, ranitidine hydrochloride. The obtained time-resolved Raman peaks were identified based on the calculations and existing literature. Raman spectra using non-time-resolved setups with continuous-wave 785- and 532-nm excitation lasers were used as reference data. Overall, this demonstration of time-resolved Raman and fluorescence measurements with a CMOS SPAD detector shows promise in diverse areas, including fundamental chemical research, the pharmaceutical setting, process analytical technology (PAT), and the life sciences.