Self-passivation of Halide Interstitial Defects by Organic Cations in Hybrid Lead-Halide Perovskites: Ab Initio Quantum Dynamics
- Award ID(s):
- 2154367
- PAR ID:
- 10583511
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 146
- Issue:
- 42
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 29255 to 29265
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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We present a combined experimental and density functional theory study that characterizes the charge and spin density in NiX2(3,5-lutidine)4(X= Cl, Br and I). In this material, magnetic exchange interactions occur via Ni2+–halide...halide–Ni2+pathways, forming one-dimensional chains. We find evidence for weak halide...halide covalency in the iodine system, which is greatly reduced whenX= Br and is absent forX= Cl; this is consistent with the reported `switching-on' of magnetic exchange in the larger-halide cases. Our results are benchmarked against density functional theory calculations on [NiHF2(pyrazine)2]SbF6, in which the primary magnetic exchange is mediated by F–H–F bridging ligands. This comparison indicates that, despite the largely depleted charge density found at the centre of halide...halide bonds, these through-space interactions can support strong magnetic exchange gated by weak covalency and enhanced by significant electron density overlapping that of the transition metal centres.more » « less
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