Extension of molecules with an inverted singlet-triplet gap with conjugated branches to alter the oscillator strength.

Molecules that violate Hund's rule and possess negative singlet-triplet gaps (ΔEST) have been actively studied for their potential usage in organic light emitting diodes without the need for thermal activation. However, the weak oscillator strength from the symmetry of such molecules has been recognized as their shortcoming for their application in optoelectronic devices. A group of molecules with a common structural motif involving the original molecule with an inverted gap having branches consisting of conjugated molecules of varied structures and extent of conjugation have been predicted to have desirable oscillator strength, but only few detailed and comprehensive studies regarding the form of excited states and the reason behind the improved oscillator strength have been carried out. We show in this work a series of analyses that suggest that the increase of oscillator strength is correlated with the nature of the excited state changing from a localized excitation to a delocalized excitation involving the central molecule and the branches. The resulting oscillator strength thus depends on the energetic matching of the branching molecule and the central molecule, rather than solely the oscillator strength of the central molecule. From the ΔEST inversion point of view, the static correlation with low-lying doubly excited configurations, the key mechanism behind the inversion in the localized excited state, weakens as the excited states delocalize. As a consequence, the dynamic correlation has a more decisive effect in determining the singlet-triplet gap.

Calculation of exciton couplings based on density functional tight-binding coupled to state-interaction state-averaged ensemble-referenced Kohn-Sham approach.

We introduce the combination of the density functional tight binding (DFTB) approach, including onsite correction (OC) and long-range corrected (LC) functional and the state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method with extended active space involving four electrons and four orbitals [LC-OC-DFTB/SSR(4,4)], to investigate exciton couplings in multichromophoric systems, such as organic crystals and molecular aggregates. We employ the LC-OC-DFTB/SSR(4,4) method to calculate the excitonic coupling in anthracene and tetracene. As a result, the LC-OC-DFTB/SSR(4,4) method provides a reliable description of the locally excited (LE) state in a single chromophore and the excitonic couplings between chromophores with reasonable accuracy compared to the experiment and the conventional SSR(4,4) method. In addition, the thermal fluctuation of excitonic couplings from dynamic nuclear motion in an anthracene crystal with LC-OC-DFTB/SSR(4,4) shows a similar fluctuation of excitonic coupling and spectral density with those of first-principle calculations. We conclude that LC-OC-DFTB/SSR(4,4) is capable of providing reasonable features related to LE states, such as Frenkel exciton with efficient computational cost.

Configuration mixing upon reorganization of dihedral angle induces rapid intersystem crossing in organic photoredox catalyst.

A long excited state lifetime is a desirable quality of photocatalysts because it enables a higher probability of energy or electron transfer from the photocatalyst to a substrate. However, achieving a long lifetime in organic (metal-free) catalysts is challenged by competing rapid nonradiative relaxation from excited states and relatively slow intersystem crossing into long-lived states with different spin multiplicity. In this work, we propose an intersystem crossing mechanism in heavy-metal free photocatalyst that results from reorganization of a dihedral angle between moieties. The relaxation of orthogonality of the dihedral angle and increasing the orbital overlap between the two components of the molecule changes the coupling between the configurations of singlet and triplet states, which in turn results in larger spin orbit coupling between the two manifolds as the molecule twists. We predict that this enables intersystem crossing to outcompete the singlet state lifetime.

Triplet Energy Transfer Governs the Dissociation of the Correlated Triplet Pair in Exothermic Singlet Fission.

Singlet fission is a spin-allowed process of exciton multiplication that has the potential to enhance the efficiency of photovoltaic devices. The majority of studies to date have emphasized understanding the first step of singlet fission, where the correlated triplet pair is produced. Here, we examine separation of correlated triplet pairs. We conducted temperature-dependent transient absorption on 6,3-bis(tri isopropylsilylethynyl)pentacene (TIPS-Pn) films, where singlet fission is exothermic. We evaluated time constants to show that their temperature dependence is inconsistent with an exclusively thermally activated process. Instead, we found that the trends can be modeled by a triplet-triplet energy transfer. The fitted reorganization energy and electronic coupling agree closely with values calculated using density matrix renormalization group quantum-chemical theory. We conclude that dissociation of the correlated triplet pair to separated (but spin-entangled) triplet excitons in TIPS-Pn occurs by triplet-triplet energy transfer with a hopping time constant of approximately 3.5 ps at room temperature.

Tuberculosis prevention and care in Korea: Evolution of policy and practice.

Tuberculosis (TB) in Korea remains a serious health problem with an estimated 77 per 100,000 incidence rate for 2016. This makes Korea as the only OECD country with high incidence of TB. The government has increased budgets and strengthened patient management policies since 2011. The management of latent tuberculosis was added to the response with strengthened and extensive contact investigations in the five-year tuberculosis control plan (2013-2017) and implementation was established in 2013. Due to these efforts Korea has achieved an average 5.2% reduction annually in tuberculosis incidence rate between 2011 and 2016. To further expedite the reduction of the TB burden the government has introduced additional measures including mandatory screening of latent tuberculosis infection for community workers in congregate settings including daycare centers for children, kindergarten, and teachers in schools and health care workers in clinics and hospitals to solve the problems identified through contact investigations in 2017. Providing high quality free diagnosis and treatment of active TB including for multidrug resistant TB combined with active contact investigations is the mainstay of the current programmatic response in Korea. However, the limitation of existing tools for LTBI pose challenge including absence of best mechanism for effective communication with professionals and the public, the need for at least 3 months of treatment and the risk of side effects. Developing effective tools will help to overcome these challenges.

Peeling the onion: a revised model of the electron count for matryoshka clusters.

We have provided a model for understanding two isoelectronic matryoshka clusters, [Sn@Cu12@Sn20](12-) and [As@Ni12@As20](3-). By dividing each of the clusters in a layer-by-layer manner and allowing each layer to follow a simple electron-filling rule, we can formulate a consistent model to explain experimental and computed properties of both matryoshka clusters that cannot be adequately explained by existing models. By analysing these clusters in a way analogous to peeling an onion, we can not only have an understanding of the structure and bonding of the two matryoshka clusters under study, but also have a generalizable model to handle certain p/d-block@d-block endohedral clusters.