Issue 19, 2024

Optical study of Te8 ring clusters: comparison with density functional theory and a step towards materials design using nanoporous zeolite space

Abstract

The Te8 ring molecule (cluster) is poorly investigated due to the lack of experimental data. Here, we report an experimental and theoretical study of a regular array of oriented Te8 rings formed in the ∼1.14 nm diameter cavities of zeolite LTA, which are arranged in a cubic lattice with a spacing of ∼1.2 nm. Single crystals of LTA with encapsulated tellurium (LTA-Te) were studied using Raman spectroscopy (RS) and optical absorption spectroscopy (OAS). The experimental LTA-Te spectra were found to be in agreement with those calculated using density functional theory (PBE0 hybrid functional and def2-TZVP basis sets) for the crown-shaped Te8 ring molecule with D4d symmetry. Using polarization–orientation RS, we show that the Te8 rings are oriented by their major axes along the 4-fold axes of cubic LTA. We also show that the site symmetry of Te8 in LTA-Te is lower than D4d. Te8 bond-bending modes are well described in the harmonic approximation, while bond-stretching modes are mixed due to the reduced ring symmetry and, probably, anharmonicity. Importantly, OAS data of LTA-Te display dependence on the Te8 concentration, implying the interaction of the rings from neighbouring LTA cavities with the generation of the valence and conduction electron bands of such a cluster crystal.

Graphical abstract: Optical study of Te8 ring clusters: comparison with density functional theory and a step towards materials design using nanoporous zeolite space

Article information

Article type
Paper
Submitted
09 Janv. 2024
Accepted
12 Apr. 2024
First published
13 Apr. 2024

Nanoscale, 2024,16, 9436-9446

Optical study of Te8 ring clusters: comparison with density functional theory and a step towards materials design using nanoporous zeolite space

V. Poborchii and D. Rappoport, Nanoscale, 2024, 16, 9436 DOI: 10.1039/D4NR00114A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements