37 research outputs found
Donor-Acceptor Substituted Benzo-, Naphtho- and Phenanthro-Fused Norbornadienes
The photochromic norbornadiene/quadricyclane (NBD/QC) couple has found interest as a molecular solar thermal energy (MOST) system for storage of solar energy. To increase the energy difference between the two isomers, we present here the synthesis of a selection of benzo-fused NBD derivatives that contain an aromatic unit, benzene, naphthalene or phenanthrene, fused to one of the NBD double bonds, while the carbon atoms of the other double bond are functionalized with donor and acceptor groups. The synthesis protocols involve functionalization of benzo-fused NBDs with bromo/chloro substituents followed by a subjection of these intermediates to a cyanation reaction (introducing a cyano acceptor group) followed by a Sonogashira coupling (introducing an arylethynyl donor group, -CCC6H4NMe2 or -CCC6H4OMe). While the derivatives have good absorption properties in the visible region (redshifted relative to parent system) in the context of MOST applications, they lack the ability to undergo NBD-to-QC photoisomerization, even in the presence of a photosensitizer. It seems that loss of aromaticity of the fused aromatics is too significant to allow photoisomerization to occur. The concept of destroying aromaticity of a neighboring moiety as a way to enhance the energy density of the NBD/QC couple thus needs further structural modifications, in the quest for optimum MOST systems
Molecular solar thermal energy storage in photoswitch oligomers increases energy densities and storage times
Molecular photoswitches can be used for solar thermal energy storage by photoisomerization into high-energy, meta-stable isomers; we present a molecular design strategy leading to photoswitches with high energy densities and long storage times. High measured energy densities of up to 559 kJ kg(-1) (155 Wh kg(-1)), long storage lifetimes up to 48.5 days, and high quantum yields of conversion of up to 94% per subunit are demonstrated in norbornadiene/quadricyclane (NBD/QC) photo-/thermoswitch couples incorporated into dimeric and trimeric structures. By changing the linker unit between the NBD units, we can at the same time fine-tune light-harvesting and energy densities of the dimers and trimers so that they exceed those of their monomeric analogs. These new oligomers thereby meet several of the criteria to be met for an optimum molecule to ultimately enter actual devices being able to undergo closed cycles of solar light-harvesting, energy storage, and heat release
Underlying Event measurements in pp collisions at and 7 TeV with the ALICE experiment at the LHC
Heteroaryl-linked norbornadiene dimers with redshifted absorptions
Development of Molecular Solar Thermal (MOST) systems for harvesting and storing solar energy is based on molecular photoswitches that undergo photoisomerizations to metastable isomers. One challenge is to achieve low-molecular weight molecules that absorb at sufficiently long wavelengths to match the solar spectrum. Here we show that this can be achieved by linking two norbornadiene (NBD) photoswitches to a central heterocycle, thiophene or carbazole, via alkyne appendages. In this approach, the same heteroaryl is used to tune the properties of two photoswitches at the same time, thereby keeping the molecular weight as low as possible. A series of NBD dimers was prepared by Sonogashira coupling reactions, and these compounds showed remarkable redshifted absorptions, with onsets of absorption as high as 468 nm, and thermal half-lives ranging from 44 seconds to 16 hours
Norbornadiene-Based Photoswitches with Exceptional Combination of Solar Spectrum Match and Long-Term Energy Storage
Norbornadiene-quadricyclane (NBD-QC) photoswitches are candidates for applications in solar thermal energy storage. Functionally, they rely on an intramolecular [2+2] cycloaddition reaction, which couples the S0 landscape on the NBD side to the S1 landscape on the QC side of the reaction and vice-versa. This commonly results in an unfavourable correlation between the first absorption maximum and the barrier for thermal back-conversion. This work demonstrates that this correlation can be counteracted by using steric repulsion to hamper the rotational motion of the side groups along the back-conversion path. It is shown that this modification reduces the correlation between the effective back-conversion barrier and the first absorption maximum and also increases the back-conversion entropy. The resulting molecules exhibit exceptionally long half-lives for their metastable forms without significantly affecting other properties, most notably solar spectrum match and storage density
Where Brain, Body and World Collide
The production cross section of electrons from semileptonic decays of beauty hadrons was measured at mid-rapidity (|y| < 0.8) in the transverse momentum range 1 < pt < 8 Gev/c with the ALICE experiment at the CERN LHC in pp collisions at a center of mass energy sqrt{s} = 7 TeV using an integrated luminosity of 2.2 nb^{-1}. Electrons from beauty hadron decays were selected based on the displacement of the decay vertex from the collision vertex. A perturbative QCD calculation agrees with the measurement within uncertainties. The data were extrapolated to the full phase space to determine the total cross section for the production of beauty quark-antiquark pairs
Long-range angular correlations of π, K and p in p–Pb collisions at = 5.02 TeV
Angular correlations between unidentified charged trigger particles and various species of charged associated particles (unidentified particles, pions, kaons, protons and antiprotons) are measured by the ALICE detector in p-Pb collisions at a nucleon--nucleon centre-of-mass energy of 5.02 TeV in the transverse-momentum range 0.3 < < 4 GeV/c. The correlations expressed as associated yield per trigger particle are obtained in the pseudorapidity range || < 0.8. Fourier coefficients are extracted from the long-range correlations projected onto the azimuthal angle difference and studied as a function of and in intervals of event multiplicity. In high-multiplicity events, the second-order coefficient for protons, , is observed to be smaller than that for pions, , up to about = 2 GeV/c. To reduce correlations due to jets, the per-trigger yield measured in low-multiplicity events is subtracted from that in high-multiplicity events. A two-ridge structure is obtained for all particle species. The Fourier decomposition of this structure shows that the second-order coefficients for pions and kaons are similar. The is found to be smaller at low and larger at higher than , with a crossing occurring at about 2 GeV. This is qualitatively similar to the elliptic-flow pattern observed in heavy-ion collisions. A mass ordering effect at low transverse momenta is consistent with expectations from hydrodynamic model calculations assuming a collectively expanding system.Angular correlations between unidentified charged trigger particles and various species of charged associated particles (unidentified particles, pions, kaons, protons and antiprotons) are measured by the ALICE detector in p-Pb collisions at a nucleon-nucleon centre-of-mass energy of 5.02 TeV in the transverse-momentum range GeV/. The correlations expressed as associated yield per trigger particle are obtained in the pseudorapidity range . Fourier coefficients are extracted from the long-range correlations projected onto the azimuthal angle difference and studied as a function of and in intervals of event multiplicity. In high-multiplicity events, the second-order coefficient for protons, , is observed to be smaller than that for pions, , up to about GeV/. To reduce correlations due to jets, the per-trigger yield measured in low-multiplicity events is subtracted from that in high-multiplicity events. A two-ridge structure is obtained for all particle species. The Fourier decomposition of this structure shows that the second-order coefficients for pions and kaons are similar. The is found to be smaller at low and larger at higher than , with a crossing occurring at about 2 GeV. This is qualitatively similar to the elliptic-flow pattern observed in heavy-ion collisions. A mass ordering effect at low transverse momenta is consistent with expectations from hydrodynamic model calculations assuming a collectively expanding system.Angular correlations between unidentified charged trigger particles and various species of charged associated particles (unidentified particles, pions, kaons, protons and antiprotons) are measured by the ALICE detector in p–Pb collisions at a nucleon–nucleon centre-of-mass energy of 5.02 TeV in the transverse-momentum range 0.3<pT<4 GeV/c . The correlations expressed as associated yield per trigger particle are obtained in the pseudorapidity range |ηlab|<0.8 . Fourier coefficients are extracted from the long-range correlations projected onto the azimuthal angle difference and studied as a function of pT and in intervals of event multiplicity. In high-multiplicity events, the second-order coefficient for protons, v2p , is observed to be smaller than that for pions, v2π , up to about pT=2 GeV/c . To reduce correlations due to jets, the per-trigger yield measured in low-multiplicity events is subtracted from that in high-multiplicity events. A two-ridge structure is obtained for all particle species. The Fourier decomposition of this structure shows that the second-order coefficients for pions and kaons are similar. The v2p is found to be smaller at low pT and larger at higher pT than v2π , with a crossing occurring at about 2 GeV/c . This is qualitatively similar to the elliptic-flow pattern observed in heavy-ion collisions. A mass ordering effect at low transverse momenta is consistent with expectations from hydrodynamic model calculations assuming a collectively expanding system