Scintillation and optical properties of xenon-doped liquid argon

Liquid argon (LAr) is a common choice as detection medium in particle physics and rare-event searches. Challenges of LAr scintillation light detection include its short emission wavelength, long scintillation time and short attenuation length. The addition of small amounts of xenon to LAr is known to improve the scintillation and optical properties. We present a characterization campaign on xenon-doped liquid argon (XeDLAr) with target xenon concentrations ranging from 0 to 300 ppm by mass encompassing the measurement of the photoelectron yield Y, effective triplet lifetime τ 3 and effective attenuation length λ att. The measurements were conducted in the Subterranean Cryogenic ARgon Facility, Scarf, a 1 t (XeD)LAr test stand in the shallow underground laboratory (UGL) of TU-Munich. These three scintillation and optical parameters were observed simultaneously with a single setup, the Legend Liquid Argon Monitoring Apparatus, Llama. The actual xenon concentrations in the liquid and gaseous phases were determined with the Impurity DEtector For Investigation of Xenon, Idefix, a mass spectrometer setup, and successful doping was confirmed. At the highest dopant concentration we find a doubling of Y, a tenfold reduction of τ 3 to ∼90 ns and a tenfold increase of λ att to over 6 m.

Spin crossover of thiophosgene via multidimensional heavy-atom quantum tunneling

The spin-crossover reaction of thiophosgene has drawn broad attention from both experimenters and theoreticians as a prime example of radiationless intramolecular decay via intersystem crossing. Despite multiple attempts over 20 years, theoretical predictions have typically been orders of magnitude in error relative to the experimentally measured triplet lifetime. We address the T1 → S0 transition by the first application of semiclassical golden-rule instanton theory in conjunction with on-the-fly electronic-structure calculations based on multireference perturbation theory. Our first-principles approach provides excellent agreement with the experimental rates. This was only possible due to the fact that instanton theory goes beyond previous methods by locating the optimal tunneling pathway in full dimensionality and thus captures "corner cutting" effects. Since the reaction is situated in the Marcus inverted regime, the tunneling mechanism can be interpreted in terms of two classical trajectories, one traveling forwards and one backwards in imaginary time, which are connected by particle--antiparticle creation and annihilation events. The calculated mechanism indicates that the spin crossover is sped up by many orders of magnitude due to multidimensional quantum tunneling of the carbon atom even at room temperature.

Atomically resolved single-molecule triplet quenching

The nonequilibrium triplet state of molecules plays an important role in photocatalysis, organic photovoltaics, and photodynamic therapy. We report the direct measurement of the triplet lifetime of an individual pentacene molecule on an insulating surface with atomic resolution by introducing an electronic pump-probe method in atomic force microscopy. Strong quenching of the triplet lifetime is observed if oxygen molecules are coadsorbed in close proximity. By means of single-molecule manipulation techniques, different arrangements with oxygen molecules were created and characterized with atomic precision, allowing for the direct correlation of molecular arrangements with the lifetime of the quenched triplet. Such electrical addressing of long-lived triplets of single molecules, combined with atomic-scale manipulation, offers previously unexplored routes to control and study local spin-spin interactions.

Elongation of Triplet Lifetime Caused by Intramolecular Energy Hopping in Diphenylanthracene Dyads Oriented to Undergo Efficient Triplet–Triplet Annihilation Upconversion

Triplet–triplet annihilation (TTA)-assisted photon upconversion (TTA-UC) in three dyads (DPA–Cn–DPA), comprised of two diphenylanthracene (DPA) moieties connected by nonconjugated C1, C2, and C3 linkages (Cn), has been investigated. The performance of these dyads as energy acceptors in the presence of the energy donor platinum octaethylporphyrin are characterized by longer triplet lifetimes (<i>τ</i>_T) and different TTA rate constants than those of the parent DPA. The larger <i>t</i>_T of the linked systems, caused by “Intramolecular Energy Hopping” in the triplet dyad ³DPA*–Cn–DPA, results in a low threshold intensity, a key characteristic of efficient TTA-UC.

Why Triage the Materials with Low Luminescence Quantum Efficiency: The Use of 35Cbz4BzCN as a Universal Host for Organic Light Emitting Diode through Effective Triplet Energy Transfer

35Cbz4BzCN, a novel universal host with long triplet lifetime, has been developed. The triplet excitons in 35Cbz4BzCN can be effectively harvested by phosphorescence and thermally activated delayed fluorescence emitters. In...

A Universal Thermally Activated Delayed Fluorescence Host with Short Triplet Lifetime for Highly Efficient Phosphorescent OLEDs with Extremely Low Efficiency Roll-off

Triplet-involved quenching processes lead to significant efficiency roll-off in phosphorescent organic light-emitting diodes (OLEDs). Thermally activated delayed fluorescence (TADF) materials can reduce the triplet exciton density in the emitting layer...

Controlling Singlet Fission with Coordination Chemistry-Induced Assembly of Dipyridyl Pyrrole Bipentacenes

Singlet fission has the potential to surpass current efficiency limits in next-generation photovoltaics and to find use in quantum information science. Despite the demonstration of singlet fission in various materials, there is still a great need for fundamental design principles that allow for tuning of photophysical parameters, including the rate of fission and triplet lifetimes. Here we describe the synthesis and photophysical characterization of a novel bipentacene dipyridyl pyrrole (HDPP-Pent) and its Li- and K-coordinated derivatives. HDPP-Pent undergoes singlet fission at roughly 50% efficiency (τ_SF = 730 ps), whereas coordination in the Li complex induces significant structural changes to generate a dimer, resulting in a 5-fold rate increase (τ_SF = 140 ps) and near fully efficient singlet fission with virtually no sacrifice in triplet lifetime. We thus illustrate novel design principles to produce favorable singlet fission properties, wherein through-space control can be achieved via coordination chemistry-induced multi-pentacene assembly.

Controlling Singlet Fission with Coordination Chemistry-Induced Assembly of Dipyridyl Pyrrole Bipentacenes

Singlet fission has the potential to surpass current efficiency limits in next-generation photovoltaics and to find use in quantum information science. Despite the demonstration of singlet fission in various materials, there is still a great need for fundamental design principles that allow for tuning of photophysical parameters, including the rate of fission and triplet lifetimes. Here we describe the synthesis and photophysical characterization of a novel bipentacene dipyridyl pyrrole (HDPP-Pent) and its Li- and K-coordinated derivatives. HDPP-Pent undergoes singlet fission at roughly 50% efficiency (τ_SF = 730 ps), whereas coordination in the Li complex induces significant structural changes to generate a dimer, resulting in a 5-fold rate increase (τ_SF = 140 ps) and near fully efficient singlet fission with virtually no sacrifice in triplet lifetime. We thus illustrate novel design principles to produce favorable singlet fission properties, wherein through-space control can be achieved via coordination chemistry-induced multi-pentacene assembly.