Details
| Original language | English |
|---|---|
| Pages (from-to) | 8158-8176 |
| Number of pages | 19 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 26 |
| Issue number | 10 |
| Early online date | 14 Feb 2024 |
| Publication status | Published - 2024 |
Abstract
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.
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In: Physical Chemistry Chemical Physics, Vol. 26, No. 10, 2024, p. 8158-8176.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Photo-excited charge transfer from adamantane to electronic bound states in water
AU - Wang, Xiangfei
AU - Krause, Pascal
AU - Kirschbaum, Thorren
AU - Palczynski, Karol
AU - Dzubiella, Joachim
AU - Bande, Annika
N1 - Funding Information: X. W.'s work receives support from the Chinese Scholar Council (CSC). T. K. acknowledges the support from the Helmholtz Einstein International Berlin Research School in Data Science (HEIBRiDS). The computing resources come from the Freie Universität Berlin (HPC cluster Curta87) and the Dirac HPC of the Helmholtz-Zentrum Berlin.
PY - 2024
Y1 - 2024
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85186214418&partnerID=8YFLogxK
U2 - 10.1039/d3cp04602h
DO - 10.1039/d3cp04602h
M3 - Article
AN - SCOPUS:85186214418
VL - 26
SP - 8158
EP - 8176
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 10
ER -