Massive Stokes shift in 12-coordinate Ce(NO2)6 3−: crystal structure, vibrational and electronic spectra

Yuxia Luo; Chun-Kit Hau; Yau Yuen Yeung; Ka-Leung Wong; Kwok Keung Shiu; Peter A. Tanner

doi:10.1038/s41598-018-34889-4

Massive Stokes shift in 12-coordinate Ce(NO2)₆ ³⁻: crystal structure, vibrational and electronic spectra

Yuxia Luo, Chun-Kit Hau, Yau Yuen Yeung, Ka-Leung Wong, Kwok Keung Shiu, Peter A. Tanner

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

4 Citations (Scopus)

Abstract

The Ce³⁺ ion in Cs₂NaCe(NO₂)₆ (I), which comprises the unusual T_h site symmetry of the Ce(NO₂)₆ ³⁻ ion, demonstrates the largest Ce-O Stokes shift of 8715 cm⁻¹ and the low emission quenching temperature of 53 K. The activation energy for quenching changes with temperature, attributed to relative shifts of the two potential energy curves involved. The splitting of the Ce³⁺ 5d¹ state into two levels separated by 4925 cm⁻¹ is accounted for by a first principles calculation using the crystal structure data of I. The NO₂ ⁻ energy levels and spectra were investigated also in Cs₂NaLa(NO₂)₆ and modelled by hybrid DFT. The vibrational and electronic spectral properties have been thoroughly investigated and rationalized at temperatures down to 10 K. A comparison of Stokes shifts with other Ce-O systems emphasizes the dependence upon the coordination number of Ce³⁺. © 2018, The Author(s).

Original language	English
Article number	16557
Journal	Scientific Reports
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41598-018-34889-4
Publication status	Published - 1 Dec 2018
Externally published	Yes

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Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Funding

Y.Y.Y. acknowledges internal funding from the Education University of Hong Kong. K.L.W. acknowledges grants from The Hong Kong Research Grants Council (HKBU 22301615), Hong Kong Baptist University (FRG 2/17-18/007) and Prospective Joint Research Project (BY2015042-01).

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This full text is made available under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/

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title = "Massive Stokes shift in 12-coordinate Ce(NO2)6 3−: crystal structure, vibrational and electronic spectra",

abstract = "The Ce3+ ion in Cs2NaCe(NO2)6 (I), which comprises the unusual Th site symmetry of the Ce(NO2)6 3− ion, demonstrates the largest Ce-O Stokes shift of 8715 cm−1 and the low emission quenching temperature of 53 K. The activation energy for quenching changes with temperature, attributed to relative shifts of the two potential energy curves involved. The splitting of the Ce3+ 5d1 state into two levels separated by 4925 cm−1 is accounted for by a first principles calculation using the crystal structure data of I. The NO2 − energy levels and spectra were investigated also in Cs2NaLa(NO2)6 and modelled by hybrid DFT. The vibrational and electronic spectral properties have been thoroughly investigated and rationalized at temperatures down to 10 K. A comparison of Stokes shifts with other Ce-O systems emphasizes the dependence upon the coordination number of Ce3+. {\textcopyright} 2018, The Author(s).",

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AU - Wong, Ka-Leung

AU - Shiu, Kwok Keung

AU - Tanner, Peter A.

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N2 - The Ce3+ ion in Cs2NaCe(NO2)6 (I), which comprises the unusual Th site symmetry of the Ce(NO2)6 3− ion, demonstrates the largest Ce-O Stokes shift of 8715 cm−1 and the low emission quenching temperature of 53 K. The activation energy for quenching changes with temperature, attributed to relative shifts of the two potential energy curves involved. The splitting of the Ce3+ 5d1 state into two levels separated by 4925 cm−1 is accounted for by a first principles calculation using the crystal structure data of I. The NO2 − energy levels and spectra were investigated also in Cs2NaLa(NO2)6 and modelled by hybrid DFT. The vibrational and electronic spectral properties have been thoroughly investigated and rationalized at temperatures down to 10 K. A comparison of Stokes shifts with other Ce-O systems emphasizes the dependence upon the coordination number of Ce3+. © 2018, The Author(s).

AB - The Ce3+ ion in Cs2NaCe(NO2)6 (I), which comprises the unusual Th site symmetry of the Ce(NO2)6 3− ion, demonstrates the largest Ce-O Stokes shift of 8715 cm−1 and the low emission quenching temperature of 53 K. The activation energy for quenching changes with temperature, attributed to relative shifts of the two potential energy curves involved. The splitting of the Ce3+ 5d1 state into two levels separated by 4925 cm−1 is accounted for by a first principles calculation using the crystal structure data of I. The NO2 − energy levels and spectra were investigated also in Cs2NaLa(NO2)6 and modelled by hybrid DFT. The vibrational and electronic spectral properties have been thoroughly investigated and rationalized at temperatures down to 10 K. A comparison of Stokes shifts with other Ce-O systems emphasizes the dependence upon the coordination number of Ce3+. © 2018, The Author(s).

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