Details
| Original language | English |
|---|---|
| Pages (from-to) | 449-458 |
| Number of pages | 10 |
| Journal | Journal of Physical Chemistry C |
| Volume | 113 |
| Issue number | 1 |
| Publication status | Published - 8 Dec 2008 |
| Externally published | Yes |
Abstract
Fluorescence emission and excitation spectra of [Cm(H 2O) 9] 3+ ions with regular and distorted tricapped trigonal prismatic coordination geometries are reported at temperatures of 293 and 20 K. The Cm 3+ impurities are incorporated into the hexagonal crystal lattices of the isotypic [M(H 2O) 9](CF 3SO 3) 3 (M = La (1), Y (2)), and [Y(H 2O) 9](C 2H 5SO 4) 3 (3) salts, and into the low symmetry [La(H 2O) 9]Cl 3 . 15-crown-5 .H 2O (4) salt. Small but significant structural differences in the MO 9 polyhedra influence the crystal-field levels of the 8Ś 7/2 groundstate and the 6D́ 7/2 excited-state multiplets. Thus, the total 6D́ 7/2 splitting is smaller in 1-3 (376-393 cm -1) than in 4 (430 cm -1), which explains the marked blue shifts of the emission spectra of 1-3 to those of 4 and Cm 3+(aq) at 293 K. The transitions between the ground state and the two lowest crystal-field levels of the 6D́ 7/2 multiplets in 1-3 give rise to narrow fluorescence lines at the emitting level at 20 K, resolving the crystal-field levels of the ground state as sharp and narrowly spaced lines. The total ground-state splittings in 1 (8.0 cm -1), 2 (6.0 cm -1), and 3 (7.5 cm -1) are about three to four times larger than those for Cm +3 in LaCl 3 (2.0 cm -1), but four to six times smaller than those for Cm 3+ in [Y(H 2O) 8]Cl 3 . 15-crown-5 (35 cm -1). Inhomogeneous line broadening prevents resolving the ground multiplet levels in 4. Vibronic side bands associated with the 8Ś 7/2- 6D́ 7/2 transition are observed in the low temperature emission and excitation spectra. The intensities of these side bands are <1% of the parent electronic transition, the stronger ones being located below ̃400 cm -1 and correspond to various CmO 9 skeletal modes. The luminescence lifetimes in 1-4 are between 63 and 74 μs.
ASJC Scopus subject areas
- Materials Science(all)
- Electronic, Optical and Magnetic Materials
- Energy(all)
- General Energy
- Chemistry(all)
- Physical and Theoretical Chemistry
- Materials Science(all)
- Surfaces, Coatings and Films
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In: Journal of Physical Chemistry C, Vol. 113, No. 1, 08.12.2008, p. 449-458.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Optical spectra and crystal-field levels of [cm(H 2O) 9] 3+ ions with C 3h symmetry in isotypic rare-earth triflate and ethyl sulfate salts
AU - Lindqvist-Reis, Patric
AU - Walther, Clemens
AU - Klenze, Reinhardt
AU - Edelstein, Norman M.
PY - 2008/12/8
Y1 - 2008/12/8
N2 - Fluorescence emission and excitation spectra of [Cm(H 2O) 9] 3+ ions with regular and distorted tricapped trigonal prismatic coordination geometries are reported at temperatures of 293 and 20 K. The Cm 3+ impurities are incorporated into the hexagonal crystal lattices of the isotypic [M(H 2O) 9](CF 3SO 3) 3 (M = La (1), Y (2)), and [Y(H 2O) 9](C 2H 5SO 4) 3 (3) salts, and into the low symmetry [La(H 2O) 9]Cl 3 . 15-crown-5 .H 2O (4) salt. Small but significant structural differences in the MO 9 polyhedra influence the crystal-field levels of the 8Ś 7/2 groundstate and the 6D́ 7/2 excited-state multiplets. Thus, the total 6D́ 7/2 splitting is smaller in 1-3 (376-393 cm -1) than in 4 (430 cm -1), which explains the marked blue shifts of the emission spectra of 1-3 to those of 4 and Cm 3+(aq) at 293 K. The transitions between the ground state and the two lowest crystal-field levels of the 6D́ 7/2 multiplets in 1-3 give rise to narrow fluorescence lines at the emitting level at 20 K, resolving the crystal-field levels of the ground state as sharp and narrowly spaced lines. The total ground-state splittings in 1 (8.0 cm -1), 2 (6.0 cm -1), and 3 (7.5 cm -1) are about three to four times larger than those for Cm +3 in LaCl 3 (2.0 cm -1), but four to six times smaller than those for Cm 3+ in [Y(H 2O) 8]Cl 3 . 15-crown-5 (35 cm -1). Inhomogeneous line broadening prevents resolving the ground multiplet levels in 4. Vibronic side bands associated with the 8Ś 7/2- 6D́ 7/2 transition are observed in the low temperature emission and excitation spectra. The intensities of these side bands are <1% of the parent electronic transition, the stronger ones being located below ̃400 cm -1 and correspond to various CmO 9 skeletal modes. The luminescence lifetimes in 1-4 are between 63 and 74 μs.
AB - Fluorescence emission and excitation spectra of [Cm(H 2O) 9] 3+ ions with regular and distorted tricapped trigonal prismatic coordination geometries are reported at temperatures of 293 and 20 K. The Cm 3+ impurities are incorporated into the hexagonal crystal lattices of the isotypic [M(H 2O) 9](CF 3SO 3) 3 (M = La (1), Y (2)), and [Y(H 2O) 9](C 2H 5SO 4) 3 (3) salts, and into the low symmetry [La(H 2O) 9]Cl 3 . 15-crown-5 .H 2O (4) salt. Small but significant structural differences in the MO 9 polyhedra influence the crystal-field levels of the 8Ś 7/2 groundstate and the 6D́ 7/2 excited-state multiplets. Thus, the total 6D́ 7/2 splitting is smaller in 1-3 (376-393 cm -1) than in 4 (430 cm -1), which explains the marked blue shifts of the emission spectra of 1-3 to those of 4 and Cm 3+(aq) at 293 K. The transitions between the ground state and the two lowest crystal-field levels of the 6D́ 7/2 multiplets in 1-3 give rise to narrow fluorescence lines at the emitting level at 20 K, resolving the crystal-field levels of the ground state as sharp and narrowly spaced lines. The total ground-state splittings in 1 (8.0 cm -1), 2 (6.0 cm -1), and 3 (7.5 cm -1) are about three to four times larger than those for Cm +3 in LaCl 3 (2.0 cm -1), but four to six times smaller than those for Cm 3+ in [Y(H 2O) 8]Cl 3 . 15-crown-5 (35 cm -1). Inhomogeneous line broadening prevents resolving the ground multiplet levels in 4. Vibronic side bands associated with the 8Ś 7/2- 6D́ 7/2 transition are observed in the low temperature emission and excitation spectra. The intensities of these side bands are <1% of the parent electronic transition, the stronger ones being located below ̃400 cm -1 and correspond to various CmO 9 skeletal modes. The luminescence lifetimes in 1-4 are between 63 and 74 μs.
UR - http://www.scopus.com/inward/record.url?scp=65349114089&partnerID=8YFLogxK
U2 - 10.1021/jp808491k
DO - 10.1021/jp808491k
M3 - Article
AN - SCOPUS:65349114089
VL - 113
SP - 449
EP - 458
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 1
ER -