Low quantum efficiency of μ-oxo iron bisporphyrin photoacatalysts explained with femtosecond M-edge XANES

Bridged μ-oxo iron bisporphyrins serve as photocatalysts for oxidative organic transformations, but suffer from low quantum efficiency. We use femtosecond optical and M2,3-edge XANES spectroscopy to investigate the early photodynamics of the μ-oxo iron bisporphyrin, (TPPFe)2O, providing evidence for the preferential formation of an TPPFe(III)+/TPPFe(III)-O- ion pair state instead of the desired TPPFe(II)/TPPFe(IV)=O.

Revealing the contest between triplet-triplet exchange and triplet-triplet energy transfer coupling in correlated triplet pair states in singlet fission

Understanding the separation of the correlated triplet pair state 1(TT) intermediate is critical for leveraging singlet fission to improve solar cell efficiency. This separation mechanism is dominated by two key interactions: (i) the exchange interaction (K) between the triplets which leads to the spin splitting of the biexciton state into 1(TT),3(TT) and 5(TT) states, and (ii) the triplet-triplet energy transfer integral (t) which enables the formation of the spatially separated (but still spin entangled) state 1(T...T). We develop a simple ab initio technique to compute both the biexciton exchange (K) and biexciton transfer coupling. Our key findings reveal new conditions for successful correlated triplet pair state dissociation. The biexciton exchange interaction needs to be ferromagnetic or negligible to the triplet energy transfer for favourable dissociation. We also explore the effect of chromophore packing to reveal geometries where these conditions are achieved for tetracene.

Excimer formation dynamics in the isolated tetracene dimer

The understanding of excimer formation and its interplay with the singlet-correlated triplet pair state 1(TT) is of high significance for the development of efficient organic electronics. Here, we study the...

Singlet fission for quantum information and quantum computing: the parallel JDE model

Singlet fission is a photoconversion process that generates a doubly excited, maximally spin entangled pair state. This state has applications to quantum information and computing that are only beginning to be realized. In this article, we construct and analyze a spin-exciton hamiltonian to describe the dynamics of the two-triplet state. We find the selection rules that connect the doubly excited, spin-singlet state to the manifold of quintet states and comment on the mechanism and conditions for the transition into formally independent triplets. For adjacent dimers that are oriented and immobilized in an inert host, singlet fission can be strongly state-selective. We make predictions for electron paramagnetic resonance experiments and analyze experimental data from recent literature. Our results give conditions for which magnetic resonance pulses can drive transitions between optically polarized magnetic sublevels of the two-exciton states, making it possible to realize quantum gates at room temperature in these systems.