TY - JOUR
T1 - Electronic spectra and crystal-field analysis of europium in hexanitritolanthanate systems
AU - Tanner, Peter A.
AU - Li, Wenyu
AU - Ning, Lixin
PY - 2012/3/5
Y1 - 2012/3/5
N2 - The luminescence spectra of Eu 3+ at a T h point-group site in the hexanitritolanthanate systems Cs 2NaEu( 14NO 2) 6, Cs 2NaEu( 15NO 2) 6, Rb 2NaEu( 14NO 2) 6, Cs 2LiEu( 14NO 2) 6, and Cs 2NaY( 14NO 2) 6:Eu 3+ have been recorded between 19 500 and 10 500 cm -1 at temperatures down to 3 K. The spectra comprise magnetic-dipole-allowed zero phonon lines, odd-parity metal-ligand vibrations, internal anion vibrations, and lattice modes, with some weak vibrational progressions based upon vibronic origins. With the aid of density functional theory calculations, the vibrational modes in the vibronic sidebands of transitions have been assigned. The two-center transitions involving NO 2 - stretching and scissoring modes are most prominent for the 5D 0 → 7F 2 hypersensitive transition. The onset of NO 2 - triplet absorption above 20 000 cm -1 restricts the derived Eu 3+ energy-level data set to the 7F J (J = 0-6) and 5D 0,1 multiplets. A total of 21 levels have been included in crystal-field energy-level calculations of Eu 3+ in Cs 2NaEu(NO 2) 6, using seven adjustable parameters, resulting in a mean deviation of ∼20 cm -1. The comparison of our results is made with Eu 3+ in the double nitrate salt. In both cases, the fourth-rank crystal field is comparatively weaker than that in europium hexahaloelpasolites. © 2012 American Chemical Society.
AB - The luminescence spectra of Eu 3+ at a T h point-group site in the hexanitritolanthanate systems Cs 2NaEu( 14NO 2) 6, Cs 2NaEu( 15NO 2) 6, Rb 2NaEu( 14NO 2) 6, Cs 2LiEu( 14NO 2) 6, and Cs 2NaY( 14NO 2) 6:Eu 3+ have been recorded between 19 500 and 10 500 cm -1 at temperatures down to 3 K. The spectra comprise magnetic-dipole-allowed zero phonon lines, odd-parity metal-ligand vibrations, internal anion vibrations, and lattice modes, with some weak vibrational progressions based upon vibronic origins. With the aid of density functional theory calculations, the vibrational modes in the vibronic sidebands of transitions have been assigned. The two-center transitions involving NO 2 - stretching and scissoring modes are most prominent for the 5D 0 → 7F 2 hypersensitive transition. The onset of NO 2 - triplet absorption above 20 000 cm -1 restricts the derived Eu 3+ energy-level data set to the 7F J (J = 0-6) and 5D 0,1 multiplets. A total of 21 levels have been included in crystal-field energy-level calculations of Eu 3+ in Cs 2NaEu(NO 2) 6, using seven adjustable parameters, resulting in a mean deviation of ∼20 cm -1. The comparison of our results is made with Eu 3+ in the double nitrate salt. In both cases, the fourth-rank crystal field is comparatively weaker than that in europium hexahaloelpasolites. © 2012 American Chemical Society.
UR - http://www.scopus.com/inward/record.url?scp=84863230618&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84863230618&origin=recordpage
U2 - 10.1021/ic202330h
DO - 10.1021/ic202330h
M3 - RGC 21 - Publication in refereed journal
SN - 0020-1669
VL - 51
SP - 2997
EP - 3006
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -