Unknown

Dataset Information

0

Massive Stokes shift in 12-coordinate Ce(NO2)63-: 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)63- 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+.

SUBMITTER: Luo Y 

PROVIDER: S-EPMC6224556 | biostudies-other | 2018 Nov

REPOSITORIES: biostudies-other

altmetric image

Publications

Massive Stokes shift in 12-coordinate Ce(NO2)<sub>6</sub><sup>3-</sup>: crystal structure, vibrational and electronic spectra.

Luo Yuxia Y   Hau Chun-Kit CK   Yeung Yau Yuen YY   Wong Ka-Leung KL   Shiu Kwok Keung KK   Tanner Peter A PA  

Scientific reports 20181108 1


The Ce<sup>3+</sup> ion in Cs<sub>2</sub>NaCe(NO<sub>2</sub>)<sub>6</sub> (I), which comprises the unusual T<sub>h</sub> site symmetry of the Ce(NO<sub>2</sub>)<sub>6</sub><sup>3-</sup> ion, demonstrates the largest Ce-O Stokes shift of 8715 cm<sup>-1</sup> 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 Ce<sup>3+</sup> 5d<sup>1</sup> s  ...[more]

Similar Datasets

| S-EPMC3273671 | biostudies-literature
| S-EPMC3725611 | biostudies-literature
| S-EPMC6648315 | biostudies-literature
| S-EPMC2862265 | biostudies-literature
| S-EPMC3361410 | biostudies-literature
| S-EPMC2154406 | biostudies-literature
| S-EPMC4224599 | biostudies-literature
| S-EPMC2851791 | biostudies-literature
| S-EPMC4084698 | biostudies-literature
| S-EPMC5854673 | biostudies-literature