School of Chemistry - Research Publications
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ItemNo Preview AvailableA framework for multiexcitonic logic(NATURE PORTFOLIO, 2024-02)Exciton science sits at the intersection of chemical, optical and spin-based implementations of information processing, but using excitons to conduct logical operations remains relatively unexplored. Excitons encoding information could be read optically (photoexcitation-photoemission) or electrically (charge recombination-separation), travel through materials via exciton energy transfer, and interact with one another in stimuli-responsive molecular excitonic devices. Excitonic logic offers the potential to mediate electrical, optical and chemical information. Additionally, high-spin triplet and quintet (multi)excitons offer access to well defined spin states of relevance to magnetic field effects, classical spintronics and spin-based quantum information science. In this Roadmap, we propose a framework for developing excitonic computing based on singlet fission (SF) and triplet-triplet annihilation (TTA). Various molecular components capable of modulating SF/TTA for logical operations are suggested, including molecular photo-switching and multi-colour photoexcitation. We then outline a pathway for constructing excitonic logic devices, considering aspects of circuit assembly, logical operation synchronization, and exciton transport and amplification. Promising future directions and challenges are identified, and the potential for realizing excitonic computing in the near future is discussed.
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ItemNo Preview AvailableCharge Transfer-Mediated Multi-exciton Mechanisms in Weakly Coupled Perylene Dimers(AMER CHEMICAL SOC, 2023-08-21)
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ItemQuantifying the Relaxation Dynamics of Higher Electronic Excited States in Perylene.(American Chemical Society, 2023-08-31)Gating logical operations through high-lying electronic excited states presents opportunities for developing ultrafast, subnanometer computational devices. A lack of molecular systems with sufficiently long-lived higher excited states has hindered practical realization of such devices, but recent studies have reported intriguing photophysics from high-lying excited states of perylene. In this work, we use femtosecond spectroscopy supported by quantum chemical calculations to identify and quantify the relaxation dynamics of monomeric perylene's higher electronic excited states. The 21B2u state is accessed through single-photon absorption at 250 nm, while the optically dark 21Ag state is excited via the 11B3u state. Population of either state results in subpicosecond relaxation to the 11B3u state, and we quantify 21Ag and 21B2u state lifetimes of 340 and 530 fs, respectively. These lifetimes are significantly longer than the singlet fission time constant from the perylene 21B2u state, suggesting that the higher electronic states of perylene may be useful for gating logical operations.
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ItemInterexcited State Photophysics I: Benchmarking Density Functionals for Computing Nonadiabatic Couplings and Internal Conversion Rate Constants(AMER CHEMICAL SOC, 2023-01-10)We present the first benchmarking study of nonadiabatic matrix coupling elements (NACMEs) calculated using different density functionals. Using the S1 → S0 transition in perylene solvated in toluene as a case study, we calculate the photophysical properties and corresponding rate constants for a variety of density functionals from each rung of Jacob's ladder. The singlet photoluminescence quantum yield (sPLQY) is taken as a measure of accuracy, measured experimentally here as 0.955. Important quantum chemical parameters such as geometries, absorption, emission, and adiabatic energies, NACMEs, Hessians, and transition dipole moments were calculated for each density functional basis set combination (data set) using density functional theory based multireference configuration interaction (DFT/MRCI) and compared to experiment where possible. We were able to derive simple relations between the TDDFT and DFT/MRCI photophysical properties; with semiempirical damping factors of ∼0.843 ± 0.017 and ∼0.954 ± 0.064 for TDDFT transition dipole moments and energies to DFT/MRCI level approximations, respectively. NACMEs were dominated by out-of-plane derivative components belonging to the center-most ring atoms with weaker contributions from perturbations along the transverse and longitudinal axes. Calculated theoretical spectra compared well to both experiment and literature, with fluorescence lifetimes between 7.1 and 12.5 ns, agreeing within a factor of 2 with experiment. Internal conversion (IC) rates were then calculated and were found to vary wildly between 106-1016 s-1 compared with an experimental rate of the order 107 s-1. Following further testing by mixing data sets, we found a strong dependence on the method used to obtain the Hessian. The 5 characterized data sets ranked in order of most promising are PBE0/def2-TZVP, ωB97XD/def2-TZVP, HCTH407/TZVP, PBE/TZVP, and PBE/def2-TZVP.
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ItemNo Preview AvailablePhotoinitiated Energy Transfer in Porous-Cage-Stabilised Silver Nanoparticles(WILEY-V C H VERLAG GMBH, 2023-06-12)We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.