| 1. |
- Aamodt, K., et al.
(författare)
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The ALICE experiment at the CERN LHC
- 2008
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Ingår i: Journal of Instrumentation. - 1748-0221. ; 3:S08002
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Forskningsöversikt (refereegranskat)abstract
- ALICE (A Large Ion Collider Experiment) is a general-purpose, heavy-ion detector at the CERN LHC which focuses on QCD, the strong-interaction sector of the Standard Model. It is designed to address the physics of strongly interacting matter and the quark-gluon plasma at extreme values of energy density and temperature in nucleus-nucleus collisions. Besides running with Pb ions, the physics programme includes collisions with lighter ions, lower energy running and dedicated proton-nucleus runs. ALICE will also take data with proton beams at the top LHC energy to collect reference data for the heavy-ion programme and to address several QCD topics for which ALICE is complementary to the other LHC detectors. The ALICE detector has been built by a collaboration including currently over 1000 physicists and engineers from 105 Institutes in 30 countries, Its overall dimensions are 16 x 16 x 26 m(3) with a total weight of approximately 10 000 t. The experiment consists of 18 different detector systems each with its own specific technology choice and design constraints, driven both by the physics requirements and the experimental conditions expected at LHC. The most stringent design constraint is to cope with the extreme particle multiplicity anticipated in central Pb-Pb collisions. The different subsystems were optimized to provide high-momentum resolution as well as excellent Particle Identification (PID) over a broad range in momentum, up to the highest multiplicities predicted for LHC. This will allow for comprehensive studies of hadrons, electrons, muons, and photons produced in the collision of heavy nuclei. Most detector systems are scheduled to be installed and ready for data taking by mid-2008 when the LHC is scheduled to start operation, with the exception of parts of the Photon Spectrometer (PHOS), Transition Radiation Detector (TRD) and Electro Magnetic Calorimeter (EMCal). These detectors will be completed for the high-luminosity ion run expected in 2010. This paper describes in detail the detector components as installed for the first data taking in the summer of 2008.
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| 2. |
- Baryshnikov, Gleb V., et al.
(författare)
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A computational study of aromaticity and photophysical properties of unsymmetrical azatrioxa[8]circulenes
- 2017
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Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry. - 1144-0546 .- 1369-9261. ; 41:7, s. 2717-2723
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Tidskriftsartikel (refereegranskat)abstract
- Owing to their potential use in organic light-emitting diodes and field-effect transistors we present a theoretical study of a series of unsymmetrical azatrioxa[8]circulenes in order to explain the impact of outer substituents and benzoannelation on photophysical constants and aromaticity of these compounds in terms of spin-orbit coupling perturbation and magnetically-induced ring currents. It is argued that the S1-Tn inter-system crossing processes constitute the main deactivation pathways for the fluorescence quenching, something that is supported by a good agreement obtained with experimental data on fluorescence quantum yields. The concept of the gauge-including magnetically induced currents has been applied in order to estimate the role of substituents and benzoannelated fragments on the aromaticity and particularly on the overall balance between the diatropic “aromatic” and paratropic “antiaromatic” current strengths. While a variation of the substituents in the outer perimeter of the studied circulenes does not provide a clear effect on their aromaticity, it is demonstrated that an additional benzoannelation (π-extension) of the azatrioxa[8]circulene macrocycle induces a significant aromaticity enhancement.
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| 3. |
- Baryshnikov, Gleb V., et al.
(författare)
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Aromaticity and photophysics of tetrasila- and tetragerma-annelated tetrathienylenes as new representatives of the hetero[8]circulene family
- 2019
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 21:18, s. 9246-9254
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Tidskriftsartikel (refereegranskat)abstract
- 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 S-1-S-0 internal conversion is extremely slow and can not compete with the fluorescence, while the S-1-T-n inter-system crossing is a main deactivation channel of the S-1 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.
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| 4. |
- Baryshnikov, Gleb V., et al.
(författare)
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Aromaticity of the doubly charged [8]circulenes
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 18:13, s. 8980-8992
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Tidskriftsartikel (refereegranskat)abstract
- Magnetically induced current densities and current pathways have been calculated for a series of fully annelated dicationic and dianionic tetraphenylenes, which are also named [8]circulenes. The gauge including magnetically induced current (GIMIC) method has been employed for calculating the current density susceptibilities. The aromatic character and current pathways are deduced from the calculated current density susceptibilities showing that the neutral [8]circulenes have two concentric pathways with aromatic and antiaromatic character, respectively. The inner octatetraene core (the hub) is found to sustain a paratropic (antiaromatic) ring current, whereas the ring current along the outer part of the macrocycle (the rim) is diatropic (aromatic). The neutral [8]circulenes can be considered nonaromatic, because the sum of the ring-current strengths of the hub and the rim almost vanishes. The aromatic character of the doubly charged [8]circulenes is completely different: the dianionic [8]circulenes and the OC-, CH-, CH2-, SiH-, GeH-, SiH2-, and GeH2-containing dicationic species sustain net diatropic ring currents i.e., they are aromatic, whereas the O-, S-, Se-, NH-, PH- and AsH-containing dicationic [8]circulenes are strongly antiaromatic. The present study also shows that GIMIC calculations on the [8]circulenes provide more accurate information about the aromatic character than that obtained using local indices such as nuclear-independent chemical shifts (NICSs) and H-1 NMR chemical shifts.
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| 5. |
- Baryshnikov, Gleb V., et al.
(författare)
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Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 18:40, s. 28040-28051
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Tidskriftsartikel (refereegranskat)abstract
- In the present work, we studied the synergetic effect of benzoannelation and NH/O-substitution for enhancing the absorption intensity in a series of novel designed benzoannelated aza- and oxa[8]circulenes. Semi-empirical estimations of the fluorescence rate constants allowed us to determine the most promising fluorophores among all the possible benzoannelated aza-, oxa- and mixed azaoza[8]circulenes. Among them, para-dibenzoannelated [8]circulenes demonstrated the most intense light absorption and emission due to the prevailing role of the linear acene chromophore. Calculated phi(fl) values are in complete agreement with experimental data for a number of already synthesized circulenes. Thus, we believe that the most promising circulenes designed in this study can demonstrate an intensive fluorescence in the case of their successful synthesis, which in turn could be extremely useful for the fabrication of future blue OLEDs. Special attention is devoted to the aromaticity features and peculiarities of the absorption spectra for the two highly-symmetrical (D-4h ground state symmetry) pi-isoelectronic species as well as the so-called tetrabenzotetraaza[8]circulene and tetrabenzotetraoxa[8]circulene molecules. Both of them are characterized by rich electronic spectra, which can be assigned only by taking into account the vibronic coarse structure of the first electronic absorption band; the 0-1 and 0-2 transitions were found to be active in the absorption spectrum in complete agreement with experimental data obtained for both energy and intensity. The corresponding promotive vibrational modes have been determined and their vibronic activity estimated using the Franck-Condon approximation.
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| 6. |
- Baryshnikov, Gleb V., et al.
(författare)
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Optical tuning of tetrabenzo[8]circulene derivatives through pseudorotational conformational isomerization
- 2018
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Ingår i: Dyes and pigments. - : Elsevier. - 0143-7208 .- 1873-3743. ; 151, s. 372-379
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Tidskriftsartikel (refereegranskat)abstract
- In order to further search efficient [8]circulene materials for OLED applications we have theoretically investigated the structure and electronic, absorption spectra of functionalized tetrabenzo[8]circulenes with different substituents in the outer perimeter. These hydrocarbon materials complement the wide family of [8]circulenes which earlier have been demonstrated to possess promising emissive and exciplex-forming properties suitable for organic light emitting diodes. The hydrocarbon tetrabenzo[8]circulenes show saddle shape of the molecular skeleton which can exist in two different conformations with different curvatures of the macrocycle. The aromaticity, electronic structure and orbital pattern are found to be principally different for these two isomers, where the global minimum isomer is weakly antiaromatic and electronically less stable comparing with the non-aromatic local minimum structure. The absorption spectra are also very different: the global minimum structure is more active in the long-wavelength region while the local minimum isomer shows absorption only at short wavelengths. Our computational findings suggest a new concept for optical tuning of curved [8]circulenes through conformational isomerization and aromaticity control, thus through structural variations without changing the molecular composition. Based on this principle we have designed novel functionalized [8]circulenes with promising fluorescence activity.
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| 7. |
- Baryshnikov, Gleb V., et al.
(författare)
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Substituent-sensitive fluorescence of sequentially N-alkylated tetrabenzotetraaza[8]circulenes
- 2017
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Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry. - 1144-0546 .- 1369-9261. ; 41:15, s. 7621-7625
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Tidskriftsartikel (refereegranskat)abstract
- We explore the use of substituent-sensitive balance between fluorescence and non-radiative decay as a tool for optical tuning of promising materials for organic light emitting diode applications. A series of N-butylated tetrabenzotetraaza[8]circulenes is studied computationally in order to explain the gradual decrease of fluorescence intensity with the increase of the substituent number. The inter-system crossing probability is found to increase upon the gradual substitution of the circulene macrocycle as a result of the decrease of the S-1-T-1 energy gap due to the deformation of the tetrabenzotetraaza[8] circulenes and therefore the distortion of the pi-conjugation within the macrocycles. In contrast, the S-1-T-1 spin-orbit coupling matrix elements are quite insensitive to the number of outer substituents. As a result, the fluorescence-responsible pi pi(star) transition becomes less intense and the fluorescence rate constant decreases.
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| 8. |
- Baryshnikov, Gleb V., et al.
(författare)
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Vibronic absorption spectra of the angular fused bisindolo- and biscarbazoloanthracene blue fluorophores for OLED applications
- 2018
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Ingår i: Chemical Physics. - : Elsevier. - 0301-0104 .- 1873-4421. ; 513, s. 105-111
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Tidskriftsartikel (refereegranskat)abstract
- An in-depth analysis of the vibronic absorption spectra for the recently synthesized blue-fluorescent OLED emitters bis[(1,2)(5,6)]indoloanthracene and biscarbazolo[3,4-a:3',4'-h]anthracene has been carried out computationally at the density functional theory level within the Franck-Condon approximation. These molecules are characterized by extended and rich electronic absorption spectra with most absorption bands being of vibronic origin. The first excited singlet state of bis[(1,2)(5,6)]indoloanthracene compound demonstrates a clear observable double-peak vibronic progression for two different active modes in the absorption spectrum, while the S-2 state is vibronically inactive. In contrast, for the larger biscarbazolo[3,4-a:3',4'-h]anthracene compound the S-0 -> S-2 transition demonstrates well-resolved intense vibronic bands which overlap the less intense progressions of few modes in the S-0 -> S-1 transition. We have also found, that even the higher-lying and very intense S-0 -> S-4 and S-0 -> S-5 transitions for bis[(1,2)(5,6)]indoloanthracene and biscarbazolo[3,4-a:3',4'-h]anthracene, respectively, are characterized by clear vibronic progressions in excellent agreement with experimental spectra.
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| 9. |
- Karaush-Karmazin, Nataliya N., et al.
(författare)
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Impact of heteroatoms (S, Se, and Te) on the aromaticity of heterocirculenes
- 2019
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Ingår i: New Journal of Chemistry. - : ROYAL SOC CHEMISTRY. - 1144-0546 .- 1369-9261. ; 43:30, s. 12178-12190
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Tidskriftsartikel (refereegranskat)abstract
- A series of thia[7]circulenes and novel Se-, Te-, S/Te-, and Se/Te-substituted [8]circulenes have been studied by calculations of nucleus-independent chemical shift indices and gauge including magnetically induced currents to interpret the impact of heteroatoms on the aromatic properties of these polyheterocyclic species. The calculations indicate that all the studied hetero[7]circulenes and hetero[8]circulenes consist of two concentric subsystems: an inner seven- or eight-membered core is antiaromatic because of the existence of a paratropic ring current, and an outer system of benzene and hetarene rings that exhibit aromatic behaviour due to the circulation of diatropic ring currents. Thus, most of the hetero[7]circulenes can be considered as slightly antiaromatic because of the slight domination of the paratropic ring currents over the diatropic ones, whereas hetero[8]circulenes represent aromatic species due to the prevailing contribution of the diatropic currents. The antiaromaticity gradually increases with more scattered arrangements of the thiophene and benzene rings in each series of di-, tri-, tetra-, and pentathia[7]circulenes because of the reduced conjugation effect between the neighboring thiophene and benzene rings. Loss of planarity with increased strain leads to an increased antiaromatic character of the lower representatives of the thia[n]circulenes, whereas higher thia[n]circulenes demonstrate a more pronounced aromatic nature because of the small deviation from planarity. The ring current topology is found to be quite insensitive to the heteroatom type, number of hetarene rings and the size of the inner ring; this clearly manifests the special electronic structure of hetero[n]circulenes containing two concentric cyclic subsystems.
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| 10. |
- Karaush, Nataliya N., et al.
(författare)
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DFT simulation of the heteroannelated octatetraenes vibronic spectra with the Franck-Condon and Herzberg-Teller approaches including Duschinsky effect
- 2015
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Ingår i: Chemical Physics. - : Elsevier. - 0301-0104 .- 1873-4421. ; 459, s. 65-71
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Tidskriftsartikel (refereegranskat)abstract
- Calculations of vibronic structure in the electronic absorption spectra are carried out for the series of heteroannelated octatetraenes on the basis of density functional theory method. Both Franck-Condon and Herzberg-Teller approaches have been used for estimation of frequency and intensity of vibronic bands in the simulated absorption spectra with respect to the S-0 -> S-1 electronic transition. The key result discussed in this work is that the electronic transition into the first singlet excited states is vibronicallyactive in the absorption spectra for all studied circulenes in a good agreement with experimental observations. We have confirmed our previous assumption that the first (low-lying) weak absorption maximum in the spectra of tetra-tert-butyltetraoxa[8] circulene and dithieno[3,4-b: 3',4'-d]thiophene-annelated cyclooctatetraene can be assigned just for the S-0 -> S-1 transition which produce the next more intense vibronic satellite. In the case of aza[8] circulenes the S-0 -> S-1 transition is symmetry allowed and the corresponding vibronic bands are less intense relative to 0-0 band. (C) 2015 Elsevier B.V. All rights reserved.
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| 11. |
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| 12. |
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| 13. |
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| 14. |
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| 15. |
- Liberman, M. A., et al.
(författare)
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Numerical studies of curved stationary flames in wide tubes
- 2003
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Ingår i: Combustion theory and modelling. - : Informa UK Limited. - 1364-7830 .- 1741-3559. ; 7:4, s. 653-676
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Tidskriftsartikel (refereegranskat)abstract
- The nonlinear problem of the propagation of curved stationary flames in tubes of different widths is studied by means of direct numerical simulation of the complete system of hydrodynamic equations including thermal conduction, viscosity, fuel diffusion and chemical kinetics. While only a planar flame can propagate in a narrow tube of width smaller than half of the cut-off wavelength determined by the linear theory of the hydrodynamic instability of a flame front, in wider tubes stationary curved flames propagate with velocities considerably larger than the corresponding velocity of a planar flame. It is shown that only simple 'single-hump' slanted stationary flames are possible in wide tubes, and 'multi-hump' flames are possible in wide tubes only as a nonstationary mode of flame propagation. The stability limits of curved stationary flames in wider tubes and the secondary Landau-Darrieus instability are investigated. The dependence of the velocity of the stationary flame on the tube width is studied. The analytical theory describes the flame reasonably well when the tube width does not exceed some critical value. The dynamics of the flame in wider tubes is shown to be governed by a large-scale stability mechanism resulting in a highly slanted flame front. In wide tubes, the skirt of the slanted flame remains smooth with the length of the skirt and the flame velocity increasing progressively with the increase of the tube width above the second critical value. Results of the analytical theory and numerical simulations are discussed and compared with the experimental data for laminar flames in wide tubes.
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| 16. |
- Liberman, M. A., et al.
(författare)
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Self-acceleration and fractal structure of outward freely propagating flames
- 2004
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Ingår i: Physics of fluids. - : AIP Publishing. - 1070-6631 .- 1089-7666. ; 16:7, s. 2476-2482
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Tidskriftsartikel (refereegranskat)abstract
- Flame acceleration associated with development of the Landau-Darrieus hydrodynamic instability is studied by means of direct numerical simulation of the Navier-Stokes equations including chemical kinetics in the form of the Arrhenius law. The fractal excess for radially expanding flames in cylindrical geometry is evaluated. Two-dimensional (2-D) simulation of radially expanding flames in cylindrical geometry displays a radial growth with 1.25 power law temporal behavior after some transient time. It is shown that the fractal excess for 2-D geometry obtained in the numerical simulation is in good agreement with theoretical predictions. The difference in fractal dimension between 2-D cylidrical and three-dimensional spherical radially expanding flames is outlined. Extrapolation of the obtained results for the case of spherical expanding flames gives a radial growth power law that is consistent with temporal behavior obtained in the survey of experimental data.
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| 17. |
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| 18. |
- Minaev, B. F., et al.
(författare)
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Spin-orbit coupling effects in O 2 activation by cofactor-independent 2,4-dioxygenase
- 2019
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Ingår i: Ukrainian Biochemical Journal. - : Palladin Institute of Biochemistry of the NASU. - 2409-4943. ; 91:1, s. 38-46
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Tidskriftsartikel (refereegranskat)abstract
- The O 2 (dioxygen) is paramagnetic molecule with two non-paired electron spins and triplet ground state (S = 1) while majority of organic molecules are diamagnetic species; they have all electron spins paired and the singlet ground state with the total spin S = 0. Oxygenases catalyze a concerted insertion of the triplet dioxygen into organic (diamagnetic) molecules in a strictly spin-forbidden process and this puzzle is not solved so far in modern enzymology. Many oxidases and oxygenases utilize the π-conjugated organic cofactor (like flavins, pterins) in a singlet ground state and reaction of cofactor with O 2 is still spin-forbidden. It is clear that the protein environment in the enzyme active-site “helps” in some way to overcome spin prohibition, but this environment is definitely diamagnetic and the spin-puzzle still exists. Some oxidases and oxygenases use paramagnetic metal ions as a cofactor; in this case the spin prohibition is formally reduced. In recent years, a numbers of oxidative enzymes are discovered which do not contain any cofactor. In the present work, we considered a rather popular cofactor-free bacterial 2,4-dioxygenase and its oxygenolytic reactions with 2-n-alkyl-3-hydroxy-4(1H)-quinolones (AHQ’s). We presented results of quantum-chemical calculations of intermediate diradical proposed recently for direct reaction of dioxygen with AHQ substrate and made conclusion about the mechanism of spin-catalysis.
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| 19. |
- Pedersen, S. K., et al.
(författare)
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Dianthracenylazatrioxa[8]circulene : Synthesis, Characterization and Application in OLEDs
- 2021
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 27:45, s. 11609-11617
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Tidskriftsartikel (refereegranskat)abstract
- A soluble, green-blue fluorescent, π-extended azatrioxa[8]circulene was synthesized by oxidative condensation of a 3,6-dihydroxycarbazole and 1,4-anthraquinone by using benzofuran scaffolding. This is the first circulene to incorporate anthracene within its carbon framework. Solvent-dependent fluorescence and bright green electroluminescence accompanied by excimer emission are the key optical properties of this material. The presence of sliding π-stacked columns in the single crystal of dianthracenylazatrioxa[8]circulene is found to cause a very high electron-hopping rate, thus making this material a promising n-type organic semiconductor with an electron mobility predicted to be around 2.26 cm2 V−1 s−1. The best organic light-emitting diode (OLED) device based on the dianthracenylazatrioxa[8]circulene fluorescent emitter has a brightness of around 16 000 Cd m−2 and an external quantum efficiency of 3.3 %. Quantum dot-based OLEDs were fabricated by using dianthracenylazatrioxa[8]circulene as a host matrix material.
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| 20. |
- Valiev, R. R., et al.
(författare)
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First-principles calculations of anharmonic and deuteration effects on the photophysical properties of polyacenes and porphyrinoids
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 22:39, s. 22314-22323
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Tidskriftsartikel (refereegranskat)abstract
- A new method for calculating internal conversion rate constants (k_(IC)), including anharmonic effects and using the Lagrangian multiplier technique, is proposed. The deuteration effect on k_(IC) is investigated for naphthalene, anthracene, free-base porphyrin (H2P) and tetraphenylporphyrin (H2TPP). The results show that anharmonic effects are important when calculating k_(IC) for transitions between electronic states that are energetically separated (Delta E) by more than 20 000-25 000 cm(-1). Anharmonic effects are also important when Delta E < 20 000-25 000 cm(-1) and when the accepting modes are X-H stretching vibrations with a frequency larger than 2000 cm(-1). The calculations show that there is mixing between the S-1 and S-2 states of naphthalene induced by non-adiabatic interactions. The non-adiabatic interaction matrix element between the S-1 and S-2 states is 250 cm(-1) and 50 cm(-1) for the normal and fully deuterated naphthalene structure and this difference significantly affects the estimated fluorescence quantum yield. Besides aromatic hydrocarbons H2P and H2TPP, the k_(IC) rate constant is also calculated for pyrometene (PM567) and tetraoxa[8]circulene (4B) with a detailed analysis of the effect of the vibrational anharmonicity.
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