Re-examining the electronic structure of fluorescent tetra-silver clusters in zeolites

Literature Information

Publication Date 2021-01-13
DOI 10.1039/D0CP05105E
Impact Factor 3.676
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Abstract

In the present study, we have examined the electronic structures related to the fluorescence properties of small Ag42+ complexes encapsulated in zeolites. We find that interaction between Ag42+ and coordinated water molecules, which was previously proposed to be the origin of fluorescence, may not be a sufficient condition by itself. Refinement of the previously used all-silicon-cage model to include framework Al atoms leads to an asymmetric environment, and this alters the electronic structure in favor of fluorescence. We have further examined the substitution of the H2O ligands by NH3, H2S, PH3, CO and CS. Among these systems, Ag42+ binds most strongly to NH3 but the energetics for the H2S and PH3 complexes is also reasonable. The energy of the fluorescent light is related to the energy of the lowest-energy triplet state, and these energies for the H2O, NH3, H2S and PH3 systems span the range of ∼2–3 eV, i.e., roughly the visible range. Thus, the use of different ligands appears to be an attractive means for tailoring the luminescence properties.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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