Solar fuel production often starts with the energy from light being absorbed by an assembly of molecules; this electronic excitation is subsequently transferred to a suitable acceptor. For example, ...in photosynthesis, antenna complexes capture sunlight and direct the energy to reaction centres that then carry out the associated chemistry. In this Review, we describe the principles learned from studies of various natural antenna complexes and suggest how to elucidate strategies for designing light-harvesting systems. We envisage that such systems will be used for solar fuel production, to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control, or to transfer excitons over long distances. Also described are the notable properties of light-harvesting chromophores, spatial-energetic landscapes, the roles of excitonic states and quantum coherence, as well as how antennas are regulated and photoprotected.
Photoexcitation is a common strategy for initiating radical reactions in chemical synthesis. We found that photoexcitation of flavin-dependent "ene"-reductases changes their catalytic function, ...enabling these enzymes to promote an asymmetric radical cyclization. This reactivity enables the construction of five-, six-, seven-, and eight-membered lactams with stereochemical preference conferred by the enzyme active site. After formation of a prochiral radical, the enzyme guides the delivery of a hydrogen atom from flavin-a challenging feat for small-molecule chemical reagents. The initial electron transfer occurs through direct excitation of an electron donor-acceptor complex that forms between the substrate and the reduced flavin cofactor within the enzyme active site. Photoexcitation of promiscuous flavoenzymes has thus furnished a previously unknown biocatalytic reaction.
Broadband optical pump and compressed white light continuum probe were used to measure the transient excited-state absorption, ground-state bleach, and stimulated emission signals of cresyl violet ...solution in methanol. Amplitude oscillations caused by wavepacket motion in the ground and excited electronic states were analyzed. It was found that vibrational coherences in the excited state persist for more than the experimental waiting time window of 6 ps, and the strongest mode had a dephasing time constant of 2.4 ps. We hypothesize the dephasing of the wavepacket in the excited state is predominantly caused by intramolecular vibrational relaxation (IVR). Slow IVR indicates weak mode–mode coupling and therefore weak anharmonicity of the potential of this vibration. Thus, the initially prepared vibrational wavepacket in the excited state is not significantly perturbed by nonadiabatic coupling to other electronic states, and hence the diabatic and adiabatic representations of the system are essentially identical within the Born–Oppenheimer approximation. The wavepacket therefore evolves with time in an almost harmonic potential, slowly dephased by IVR and the pure vibrational decoherence. The consistency in the position of node (phase change in the wavepacket) in the excited-state absorption and stimulated emission signals without undergoing any frequency shift until the wavepacket is completely dephased conforms to the absence of any reactive internal conversion.
Long-range interactions between biomacromolecules are considered important for directing intracellular processes. Recent studies have posited that interactions between oscillating dipoles are ...well-suited to mediating long-range forces because they are weakly screened by a dielectric environment. Here, we extend these studies and present a quantum electrodynamic mechanism for resonant interactions between vibrational transition dipole moments of molecules. We explicitly consider the molecular charge density oscillations as IR transition dipoles. This gives a physical, molecular assignment to the idea of oscillating dipoles and allows us to develop explicit expressions for the interactions that can be quantified using parameters known from experiment. Moreover, in the same framework, we can describe van der Waals forces. We use numerical calculations to estimate the strength of resonant vibrational dipole–dipole interactions over long distances and compare these estimates to the van der Waals interaction. We find that the resonant vibrational dipole–dipole interactions dominate over the long range.
We report mechanistic insights into an iridium/nickel photocatalytic C–O cross-coupling reaction from time-resolved spectroscopic studies. Using transient absorption spectroscopy, energy transfer ...from an iridium photocatalyst to a catalytically relevant Ni(II)(aryl) acetate acceptor was observed. Concentration-dependent lifetime measurements suggest the mechanism of the subsequent reductive elimination is a unimolecular process occurring on the long-lived excited state of the Ni(II) complex. We envision that our study of the productive energy-transfer-mediated pathway would encourage the development of new excited-state reactivities in the field of metallaphotocatalysis that are enabled by light harvesting.
Quantum information, a field in which great advances have been made in the past decades, now presents opportunities for advanced chemistry. One roadblock to progress, especially for experimental ...chemical science, is that new concepts and technical definitions need to be learned. In this paper, we review some basic, but sometimes misunderstood, concepts of quantum information based on the mathematical formulation of quantum mechanics that will be useful for chemists interested in discovering ways that chemistry can contribute to the quantum information field. We cover topics including qubits and their density matrix formalism, quantum measurement as a quantum operation, information theory, and entanglement. We focus on the difference between the concepts in the quantum context and the classic context. We also discuss the relation and distinction among entanglement, correlation, and coherence. We aim to clarify the rigorous definition of these concepts and then indicate some examples in physical chemistry.
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.
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.
Waveplates are widely used in photonics to control the polarization of light1,2. Often, they are fabricated from birefringent crystals that have different refractive indices along and normal to the ...crystal axis. Similar optical components are found in the natural world, including the eyes of mantis shrimp3,4 and the iridescence of giant clams5, fish6 and plants7. Optical retardation in biology relies on sophisticated self-assembly, whereas man-made systems comprise multiple-layered materials8–11. Here we report a discovery that bridges these two design principles. We observe wideband achromatic retardation in the visible and near-infrared (532–800 nm) regions for Cs4PbBr6 perovskite crystals embedded with CsPbBr3 nanocrystals. We explain our observations as matched dispersions of the refractive indices of the ordinary and extraordinary rays caused by the ordered embedding of the nanocrystals in the host. The wideband performance and ease of fabrication of these perovskite materials are attractive for future applications.Perovskite crystals of Cs4PbBr6 embedded with CsPbBr3 nanocrystals are shown to act as wideband, achromatic waveplates in the visible and near-infrared regions.
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