Triplet Dimers Research Articles

Ground-state phase diagram of anisotropically interacting Heisenberg- Γ models on a honeycomb lattice

In this paper, we investigate the ground-state phase diagram of the $S=1/2$ Heisenberg-$\mathrm{\ensuremath{\Gamma}}$ model on a honeycomb lattice by dimer series expansion and exact diagonalization. We focus on the effects of the anisotropy of the interactions; by tuning the coupling constants, the system changes between the isolated dimer and the spin-chain models. We find that, in the spin-chain limit, there are three kinds of states: A Tomonaga-Luttinger liquid and two magnetically long-range-ordered states. All three states become two-dimensional long-range-ordered states by the infinitesimal interchain interaction except for the case where the Heisenberg interaction is much weaker than the off-diagonal symmetric $(\mathrm{\ensuremath{\Gamma}})$ interaction. Starting from the isolated dimer limit, a triplet dimer phase survives up to the isotropically interacting system in a large part of the phase diagram where the Heisenberg and $\mathrm{\ensuremath{\Gamma}}$ interactions are ferromagnetic and antiferromagnetic, respectively. Otherwise, a phase transition to a magnetically ordered phase occurs before the interaction becomes isotropic. This indicates that the quantum spin liquid proposed in the $\mathrm{\ensuremath{\Gamma}}$ model [A. Catuneanu et al., npj Quantum Mater. 3, 23 (2018)] is unstable against the anisotropy of the interactions.

Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene.

Vibronic coupling is believed to play an important role in siglet fission, wherein a photoexcited singlet exciton is converted into two triplet excitons. In the present study, we examine the role of vibronic coupling in singlet fission using polarized transient absorption microscopy and ab initio simulations on single-crystalline pentacene. It was found that singlet fission in pentacene is greatly facilitated by the vibrational coherence of a 35.0 cm-1 phonon, where anisotropic coherence persists extensively for a few picoseconds. This coherence-preserving phonon that drives the anisotropic singlet fission is made possible by a unique cross-axial charge-transfer intermediate state. In the same fashion, this phonon was also found to predominantly drive the quantum decohence of a correlated triplet pair to form a decoupled triplet dimer. Moreover, our transient kinetic experimental data illustrates notable directional anisotropicity of the singlet fission rate in single-crystalline pentacene.

Switching resonance character within merocyanine stacks and its impact on excited-state dynamics

Summary In this study, the optical properties and excited-state dynamics of the unique self-assembled donor-acceptor (DA) merocyanine dye stacks from dimer up to octamer, prepared via dipole-dipole interactions, are reported in terms of coherent exciton dynamics and formation of an excimer-like state. Our findings are based on the steady-state absorption/emission, time-resolved fluorescence, and transient absorption (anisotropy) measurements, including wavepacket analysis and quantum mechanical calculations. Coherent exciton of torsional motions-restricted dye stacks rapidly localizes into the weakly emissive excimer-like state, by shortening the inter-moiety distance and changing the bond-length alternation pattern. The inner merocyanine moiety, having two neighboring units, has a reversed resonance character (non-polar (N) Z) in the ground state. This difference has led to two conclusions: (1) tetramers and octamers exhibit different features of excimer-like state than the dimer, and (2) octamers exhibit slower localization dynamics due to the enhanced homogeneity (six inner-moieties) compared with tetramers (two inner moieties).

Annihilation Versus Excimer Formation by the Triplet Pair in Triplet-Triplet Annihilation Photon Upconversion.

The triplet pair is the key functional unit in triplet–triplet annihilation photon upconversion. The same molecular properties that stabilize the triplet pair also allow dimers to form on the singlet energy surface, creating an unwanted energy relaxation pathway. Here we show that excimer formation most likely is a consequence of a triplet dimer formed before the annihilation event. Polarity-dependent studies were performed to elucidate how to promote wanted emission pathways over excimer formation. Furthermore, we show that the yield of triplet–triplet annihilation is increased in higher-viscosity solvents. The results will bring new insights in how to increase the upconversion efficiency and how to avoid energy-loss channels.

Frustrated S = 1/2 Two-Leg Ladder with Different Leg Interactions

We explore the ground-state phase diagram of the S = 1/2 two-leg ladder. The isotropic leg interactions J1,a and J1,b between nearest neighbor spins in the legs a and b, respectively, are different from each other. The xy and z components of the uniform rung interactions are denoted by Jr and ΔJr, respectively, where Δ is the XXZ anisotropy parameter. This system has a frustration when J1,aJ1,b < 0 irrespective of the sign of Jr. The phase diagrams on the Δ (0≤Δ<1) versus J1,b plane in the cases of J1,a = − 0.2 and J1,a = 0.2 with Jr = −1 are determined numerically. We employ the physical consideration, the level spectroscopy analysis of the results obtained by the exact diagonalization method and also the density-matrix renormalization-group method. It is found that the non-collinear ferrimagnetic (NCFR) state appears as the ground state in the frustrated region of the parameters. Furthermore, the direct-product triplet-dimer (TD) state in which all rungs form the TD pair is the exact ground state, when J1,a + J1,b = 0 and 0≤ Δ ≲ 0.83. The obtained phase diagrams consist of the TD, XY and Haldane phases as well as the NCFR phase.

Strongly frustrated triangular spin lattice emerging from triplet dimer formation in honeycomb Li2IrO3.

Iridium oxides with a honeycomb lattice have been identified as platforms for the much anticipated Kitaev topological spin liquid: the spin-orbit entangled states of Ir4+ in principle generate precisely the required type of anisotropic exchange. However, other magnetic couplings can drive the system away from the spin-liquid phase. With this in mind, here we disentangle the different magnetic interactions in Li2IrO3, a honeycomb iridate with two crystallographically inequivalent sets of adjacent Ir sites. Our ab initio many-body calculations show that, while both Heisenberg and Kitaev nearest-neighbour couplings are present, on one set of Ir–Ir bonds the former dominates, resulting in the formation of spin-triplet dimers. The triplet dimers frame a strongly frustrated triangular lattice and by exact cluster diagonalization we show that they remain protected in a wide region of the phase diagram.

Almost Perfect Frustration in the Dimer Magnet Ba2CoSi2O6Cl2

We determined the crystal structure of Ba$_2$CoSi$_2$O$_6$Cl$_2$, which was synthesized in this work, and investigated its quantum magnetic properties using single crystals. This compound should be described as a two-dimensionally coupled spin-1/2 XY-like spin dimer system. Ba$_2$CoSi$_2$O$_6$Cl$_2$ exhibits a stepwise magnetization process with a plateau at half of the saturation magnetization, irrespective of the field direction, although all the Co$^{2+}$ sites are equivalent. This indicates that spin triplets are localized owing to the almost perfect frustration of interdimer exchange interactions. Thus, the spin states for the zero and 1/2 magnetization-plateau states are almost exactly given by the simple product of singlet dimers and the alternate product of singlet and triplet dimers, respectively.

Triplet–Triplet Annihilation-Induced Up-Converted Delayed Luminescence in Solid-State Organic Composites: Monitoring Low-Energy Photon Up-Conversion at Low Temperatures

Hitherto, the role of the enhanced intermolecular interactions and the effect of lowering the temperature on the process of triplet–triplet annihilation-induced up-converted delayed luminescence in solid-state composites systems have remained controversial. Here we address these issues by performing temperature-dependent time-integrated and time-gated luminescence spectroscopic studies on the model photon up-converting solid composite comprising the (2,3,7,8,12,13,17,18-octaethyl-porphyrinato) PtII (PtOEP) sensitizer, mixed with the blue-light emitting 9,10 diphenyl anthracene (DPA) activator. Atomic force microscopy imaging and photoluminescence (PL) spectra confirm that the strength of intermolecular interactions in the DPA:PtOEP system can be tuned by keeping the composite either in its binary or in its ternary form with the use of the optically inert matrix of polystyrene (PS). By diluting DPA:PtOEP in PS, the concentration of the DPA excimeric and the PtOEP triplet dimer quenching sites is reduced and the lifetime of the DPA up-converted PL signal is prolonged to the microsecond time scale. By lowering the temperature to 100 K, the DPA up-converted luminescence intensity increases by a factor of 3, and this is attributed to the increased energetic disorder of the DPA excited states in the PS:DPA:PtOEP ternary system. These findings provide useful guidelines for the fabrication of efficient solid-state photon up-converting organic layers.

Modeling pulse characteristics in Xenon with NEST

A comprehensive model for describing the characteristics of pulsed signals, generated by particle interactions in xenon detectors, is presented. An emphasis is laid on two-phase time projection chambers, but the models presented are also applicable to single phase detectors. In order to simulate the pulse shape due to primary scintillation light, the effects of the ratio of singlet and triplet dimer state populations, as well as their corresponding decay times, and the recombination time are incorporated into the model. In a two phase time projection chamber, when simulating the pulse caused by electroluminescence light, the ionization electron mean free path in gas, the drift velocity, singlet and triplet decay times, diffusion constants, and the electron trapping time, have been implemented. This modeling has been incorporated into a complete software package, which realistically simulates the expected pulse shapes for these types of detectors.

Carbazole based polymers as hosts for blue iridium emitters: synthesis, photophysics and high efficiency PLEDs

This article reports the synthesis of new carbazole based polymers and their application as hosts in sky-blue polymer light emitting devices (PLEDs) with a solution-processed emitting layer doped with a cyclometalated Ir(III) complex. We systematically investigate their effect on the PLED performance. A current efficiency of 19.7 cd A−1 and a brightness of 1850 cd m−2 were achieved with these polymers. The roll-off in electrophosphorescent quantum efficiency in PLEDs was shown to arise mainly from triplet–triplet annihilation between dopants in the hosts with tert-butyl groups. It has been shown that in the devices with hosts without tert-butyl groups the efficiency roll-off is additionally affected by electric field quenching. In these carbazole based polymers, triplet dimers are formed and tert-butyl groups do not limit the intermolecular interactions to prevent triplet dimer formation, nevertheless tert-butyl groups reduce charge transport.

Is Poly(vinylcarbazole) a Good Host for Blue Phosphorescent Dopants in PLEDs? Dimer Formation and Their Effects on the Triplet Energy Level of Poly(N‐vinylcarbazole) and Poly(N‐Ethyl‐2‐Vinylcarbazole)

AbstractThe detailed measurement and analysis of the delayed emission from poly(vinylcarbazole) (PVK) and poly(N‐ethyl‐2‐vinyl‐carbazole) (P2VK) thin films is described. PVK has rapidly become a “polymer of choice” for hosting phosphorescent dopants in PLEDs, especially blue emitters. In this respect it is important to have a full understanding of the triplet properties of this host. It is concluded that in films, the electronic 0–0 peak energy of PVK phosphorescence is found at 2.88 eV (14 K). With an increase of temperature, &gt;44 K, increasing emission from new long lived, lower energy species, previously ascribed to “trap states” in the literature, is observed. Increasing temperature enables thermally assisted triplet exciton hopping to these trap states. Critically it is shown that some of these triplet trap species are ground state triplet dimers in origin for both PVK (2.46 eV) and P2VK (2.1 eV), and not all of them are of excimer nature as previously thought. These species can quench the emission of blue heavy metal complexes doped in PVK and drastically effect performance over lifetime if the dimer formation increases over time and at elevated operating temperature. It is therefore concluded that PVK might not be such an ideal host material for blue phosphorescent emitters.

Quantum Features of a Barely Bound Molecular Dopant: Cs2(3Σu) in Bosonic Helium Droplets of Variable Size

We present in this work the study of small (4)He(N)-Cs(2)((3)Σ(u)) aggregates (2 ≤ N ≤ 30) through combined variational, diffusion Monte Carlo (DMC), and path integral Monte Carlo (PIMC) calculations. The full surface is modeled as an addition of He-Cs(2) interactions and He-He potentials. Given the negligible strength and large range of the He-Cs(2) interaction as compared with the one for He-He, a propensity of the helium atoms to pack themselves together, leaving outside the molecular dopant is to be expected. DMC calculations determine the onset of helium gathering at N = 3. To analyze energetic and structural properties as a function of N, PIMC calculations with no bosonic exchange, i.e., Boltzmann statistics, at low temperatures are carried out. At T = 0.1 K, although acceptable one-particle He-Cs(2) distributions are obtained, two-particle He-He distributions are not well described, indicating that the proper symmetry should be taken into account. PIMC distributions at T = 1 K already compare well with DMC ones and show minor exchange effects, although binding energies are still far from having converged in terms of the number of quantum beads. As N increases, the He-He PIMC pair correlation function shows a clear tendency to coincide with the experimental boson-liquid helium one at that temperature. It supports the picture of a helium droplet which carries the molecular impurity on its surface, as found earlier for other triplet dimers.

Strictly localised triplet dimers on one- and two-dimensional lattices

Electrons may form inter-site pairs (dimers) by a number of mechanisms. For example, long-range (Fröhlich) electron-phonon interactions and strong on-site Hubbard U allow formation of small light bipolarons in some lattices. We identify circumstances under which triplet dimers are strictly localised by interference in certain one- and two-dimensional lattices. We assume a U-V Hamiltonian with nearest- and next-nearest-neighbour hopping integrals t and t′, large positive U and attractive nearest- and next-nearest-neighbour interactions V and V′. In the square ladder and some two-dimensional bilayers, if the dimer Hilbert space is restricted to nearest- and next-nearest-neighbour dimers, triplet dimers become strictly localised for certain values of these parameters. For example, in a square ladder with t′ = t and V′ = V, all triplet bands become flat due to exact cancellation of hopping paths. We identify the localised eigenstates for all flat bands in each lattice. We show that many of the flat bands persist for arbitrary t/t′ so long as other restrictions still apply.

Controlling and Detecting Spin Correlations of Ultracold Atoms in Optical Lattices

We report on the controlled creation of a valence bond state of delocalized effective-spin singlet and triplet dimers by means of a bichromatic optical superlattice. We demonstrate a coherent coupling between the singlet and triplet states and show how the superlattice can be employed to measure the singlet-fraction employing a spin-blockade effect. Our method provides a reliable way to detect and control nearest-neighbor spin correlations in many-body systems of ultracold atoms. Being able to measure these correlations is an important ingredient in studying quantum magnetism in optical lattices. We furthermore employ a SWAP operation between atoms which are part of different triplets, thus effectively increasing their bond-length. Such a SWAP operation provides an important step towards the massively parallel creation of a multiparticle entangled state in the lattice.

Bi-molecular emissive excited states in platinum (II) complexes for high-performance organic light-emitting diodes

The nature of excited states in Pt(II) organic complexes used as efficient phosphorescent emitters in organic light-emitting diodes (OLEDs) is examined. These compounds were chosen because their square planar structures allow them to facially aggregate through attractive intermolecular interactions of Pt–Pt or ligand–ligand or combination of these, thereby facilitating formation of bi-molecular (B-M) states such as ground-state dimers and/or excited states – excimers and electromers. The efficient parallel emissions from B-M and mono-molecular (M-M) excited states allow to tune color and efficiency of OLEDs. Based on various spectroscopic characteristics of selected Pt L xCl complexes with different ligands L x, we find that both excited triplet dimers and excimers are formed in fluid and solid solutions in addition to monomer excitonic states, though their relative populations are strongly dependent on the sample composition and particularly on its polarity. Of two possible routes of the formation of the excimer states, the one based on molecular triplet interaction with ground state molecules is found to dominate in both optically (PL) and electrically (EL) pumped film emissions. The contribution of the direct Coulombic interaction of complex cations and anions (omitting the formation of molecular triplets) to the formation of excimers is insignificant. These findings have a direct impact on the design and general understanding of OLEDs and ultimate development of stable, high-efficiency Pt(II) organic phosphor-based LEDs. However, they apply as well to any organic material containing planar molecules or their planar parts. Thus, we would expect their importance in phthalocyanine dyes and derivitized bucky-balls that are often used in organic photovoltaics and in pentacene films that are incorporated into organic transistors.

Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

Chemiluminescence (CL) phenomenon of hydrogen peroxide with potassium permanganate in the presence of sodium hydrogen carbonate was reported. Effects of the surfactant on the CL system were investigated. Nonionic surfactants could effectively increase the CL signal. Radical scavengers and organic reagents such as nitro blue tetrazolium chloride (NBT), cytochrome c, sodium azide, ascorbic acid, thiourea, tert-butanol and dimethyl sulphoxide were used to study the emitting species. CL emission spectrum was recorded and the results showed that the maximal emission wavelengths of NaHCO3-H2O2-KMnO4 system were 440 and 634 nm. The mechanism was discussed based on electron spin resonance (ESR) spectra, fluorescence spectra and UV-vis absorption spectra. The addition of rhodamine B or uranine into this CL system enhanced the CL signal. It was due to part of the energy transfer from singlet oxygen and excited triplet dimers of two CO2 molecules to rhodamine B or uranine. The CL could be induced by excited rhodamine B or uranine.

Highly polar 7,7-bis(N,N-dimethylpiperazinium)-8,8-dicyanoquinodimethane in [Ni(dmit)2]− salt: crystal structure and magnetic properties

Highly polar 7,7-bis(N,N-dimethylpiperazinium)-8,8-dicyanoquinodimethane (BDPDQ) was introduced into the [Ni(dmit)2]− crystal as a counter cation. The (BDPDQ)[Ni(dmit)2]−2(CH3OH) crystal has two independent types of [Ni(dmit)2]− intermolecular interactions; those of π-dimers and two-dimensional layer. The magnetic properties of the crystal were explained by the sum of two types of intermolecular magnetic interactions that corresponded to singlet–triplet dimer and Curie–Weiss models.

A quantum chemistry study of Diels–Alder dimerizations in benzene and anthracene

There is considerable experimental evidence of covalent dimerization of aromatic compounds occurring under shock conditions. Because of their endothermicity, these reactions could play a large role in the shock initiation process of aromatic molecular explosives such as 2,4,6-trinitrotoluene and 1,3,5-triamino-2,4,6-trinitrobenzene by withdrawing energy from the shock compression. Very little is known about the energetics, however, and this knowledge is crucial for the design of empirical force fields that can treat shock-induced chemistry. We have employed ab initio electronic structure and density functional methods to study the Diels-Alder (DA) dimerizations of benzene and anthracene. The enthalpy of reaction for DA benzene dimerization is predicted to be +35.9 kcal/mol. The stepwise pathway to this dimer involves formation of a stable triplet intermediate that requires 71.8 kcal/mol of energy. Transition states along both the concerted and stepwise pathways were optimized and the energetics of the reaction pathways are detailed. The former is found to be the energetically preferred mechanism. Nine DA dimers of anthracene were found, with six predicted to have dimerization DeltaH(rxn)'s of 24-55 kcal/mol, two with dimerization energies near zero and one that is formed through an exothermic reaction. Twelve triplet dimers of anthracene, with DeltaH(rxn)'s ranging from 33-50 kcal/mol, are also described. Finally, the potential importance of these reactions in the context of shock compression of these materials is discussed.

Dimeric form of peroxynitrite

The (ONOO)− anion, known as peroxynitrite, is characterized by a singlet spin state. A new stable dimer form of peroxynitrite [NO-O2]− in the triplet state at distances close to r(O-N) ≈ 2.885 A between oxygen in the O2 structure and nitrogen has been established within the quantum-chemical CASSCF approximation. The vibrational motion of the dimer is significantly anharmonic; for the 16O and 14N isotopes, the differences in the energies of two neighboring levels correspond to frequencies of about 70–30 cm−1. The triplet dimer structure retains stability in the case of interaction with water molecules. The activation barriers caused by rearrangement of the peroxynitrite structure into the ground state of the NO3− anion with the symmetry D3h are found.

Trans-cis photoisomerization and photoinduced electron transfer as competitive reactions of 9-etylthiacarbocyanine in binary mixtures

The effect of the composition of the dioxane-water mixture on the ability of 9-ethylthiacarbocyanine to participate in competitive reactions of trans-cis photoisomerization and photoinduced electron transfer was studied. An increase in the dioxane content in the range 0–50 vol % leads to a shift of the equilibrium between the dye dimers and monomers toward the monomers (cis-monomers), which is accompanied by a drop in the yield of the triplet dimer molecules, which appear under the action of a laser flash, and electron-transfer products that are formed via the triplet state of dimers in the presence of methylviologen. With growing the dioxane content in the range 50–80 vol %, a shift of the equilibrium between the cis-and trans-monomers toward the trans-monomers occurs, which is accompanied by an increase in the fluorescence intensity. At the dioxane content above 80 vol %, a further shift of the equilibrium toward the trans-monomers occurs, which is accompanied by a substantial increase in the fluorescence intensity and an appearance under the action of a laser flash of the band of the triplet-triplet absorption of the trans-monomer and the absorption band of the cis-monomer as a result of trans-cis photoisomerization. The trans-monomers in the triplet state participate in the electron-transfer reaction with methylviologen. The intersystem crossing process competes with fluorescence and the trans-cis isomerization reaction, which occurs via the excited singlet state of the trans-monomers.