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Photo-excited charge transfer from adamantane to electronic bound states in water

Aqueous nanodiamonds illuminated by UV light produce free solvated electrons, which may drive high-energy reduction reactions in water. However, the influence of water conformations on the excited-state electron-transfer mechanism are still under debate. In this work, we offer a theoretical study of...

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Published in:Physical chemistry chemical physics : PCCP 2024-03, Vol.26 (1), p.8158-8176
Main Authors: Wang, Xiangfei, Krause, Pascal, Kirschbaum, Thorren, Palczynski, Karol, Dzubiella, Joachim, Bande, Annika
Format: Article
Language:English
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Summary:Aqueous nanodiamonds illuminated by UV light produce free solvated electrons, which may drive high-energy reduction reactions in water. However, the influence of water conformations on the excited-state electron-transfer mechanism are still under debate. In this work, we offer a theoretical study of charge-transfer states in adamantane-water structures obtained by linear-response time-dependent density-functional theory. Small water clusters with broken hydrogen bonds are found to efficiently bind the electron from adamantane. A distinction is made with respect to the nature of the water clusters: some bind the electron in a water cavity, others along a strong permanent total dipole. These two types of bound states are more strongly binding, the higher their electron affinity and their positive electrostatic potential, the latter being dominated by the energy of the lowest unoccupied molecular orbital of the isolated water clusters. Structural sampling in a thermal equilibrium at room temperature via molecular dynamics snapshots confirms under which conditions the underlying waters clusters can occur and verifies that broken hydrogen bonds in the water network close to adamantane can create traps for the solvated electron. Water clusters accommodate electrons from photo-excited adamantane into two types of charge-transfer states. The electron gets more strongly bound the higher the water clusters' electron affinity and their electrostatic potential.
ISSN:1463-9076
1463-9084
DOI:10.1039/d3cp04602h