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Coupling of photoactive transition metal complexes to a functional polymer matrix*.

ABSTRACT: Conductive polymers represent a promising alternative to semiconducting oxide electrodes typically used in dye-sensitized cathodes as they more easily allow a tuning of the physicochemical properties. This can then also be very beneficial for using them in light-driven catalysis. In this computational study, we address the coupling of Ru-based photosensitizers to a polymer matrix by combining two different first-principles electronic structure approaches. We use a periodic density functional theory code to properly account for the delocalized nature of the electronic states in the polymer. These ground state investigations are complemented by time-dependent density functional theory simulations to assess the Franck-Condon photophysics of the present photoactive hybrid material based on a molecular model system. Our results are consistent with recent experimental observations and allow to elucidate the light-driven redox chemical processes - eventually leading to charge separation - in the present functional hybrid systems with potential application as photocathode materials.

SUBMITTER: Putra MH

PROVIDER: S-EPMC9299502 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Multicenter transition-metal complexes (MCTMs) with magnetically interacting ions have been proposed as components for information-processing devices and storage units. For any practical application of MCTMs as magnetic units, it is crucial to characterize their magnetic behavior, and in particular, the isotropic magnetic exchange coupling, J, between its magnetic centers. Due to the large size of typical MCTMs, density functional theory is the only practical electronic structure method for evaluating the J coupling. Here, we assess the accuracy of different density functional approximations for predicting the magnetic couplings of eight dinuclear transition-metal complexes, including five dimanganese, two dicopper, and one divanadium with known reliable experimental J couplings spanning from ferromagnetic to strong antiferromagnetic. The density functionals considered include global hybrid functionals which mix semilocal density functional approximations and exact exchange with a fixed admixing parameter, six local hybrid functionals where the admixing parameters are extended to be spatially dependent, the SCAN and r2SCAN meta-generalized gradient approximations (GGAs), and two widely used GGAs. We found that global hybrids tested in this work have a tendency to over-correct the error in magnetic coupling parameters from the Perdew-Burke-Ernzerhof (PBE) GGA as seen for manganese complexes. The performance of local hybrid density functionals shows no improvement in terms of bias and is scattered without a clear trend, suggesting that more efforts are needed for the extension from global to local hybrid density functionals for this particular property. The SCAN and r2SCAN meta-GGAs are found to perform as well as benchmark global hybrids on most tested complexes. We further analyze the charge density redistribution of meta-GGAs as well as global and local hybrid density functionals with respect to that of PBE, in connection to the self-interaction error or delocalization error.

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Coupling of photoactive transition metal complexes to a functional polymer matrix*.

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