Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 5279-5285 |
| Seitenumfang | 7 |
| Fachzeitschrift | Journal of Physical Chemistry B |
| Jahrgang | 110 |
| Ausgabenummer | 11 |
| Publikationsstatus | Veröffentlicht - 1 März 2006 |
| Extern publiziert | Ja |
Abstract
The optical spectra of Cm3+ incorporated into the crystalline host structure of [Y(H2O)8]Cl3·15-crown- 5 (1) is investigated by using laser spectroscopic methods at temperatures between 20 and 293 K. The coordination geometry of the [Y(H2O) 8]3+ entity in 1 is a distorted bicapped trigonal prism with ∼C2 point symmetry, as confirmed by single-crystal X-ray diffraction at 200 K. The crystal-field splitting of the 8S' 7/2 ground state and the 6D'7/2 and 6F5/2 excited states of the hydrated Cm3+ ion are measured by high-resolution fluorescence emission and excitation spectroscopy at various temperatures. The transitions between the ground state and the respective lowest crystal-field levels of the excited states exhibit narrow fluorescence lines, resolving the four crystal-field levels of the ground state as sharp, well-resolved lines at about 0, 10, 19, and 35 cm-1. The total splittings of the 6D'7/2 and 6P'5/2 states are 670 and 170 cm-1, respectively. Thermal population of the ground-state crystal-field levels is observed and quantified in the excitation spectra in the temperature range of 20-70 K. All spectroscopic results are consistent with the presence of one unique [Cm(H2O)8]3+ site. The ground-state splitting of Cm3+ in 1, 35 cm-1, is comparable to that of Cm3+ in solid ThO2, 36 cm-1, which shows the strongest crystal field for Cm3+ reported so far. For this reason the present results are different than the findings for Ln3+ aqua ions, which show rather weak crystal field strengths.
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- Chemie (insg.)
- Physikalische und Theoretische Chemie
- Werkstoffwissenschaften (insg.)
- Oberflächen, Beschichtungen und Folien
- Werkstoffwissenschaften (insg.)
- Werkstoffchemie
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in: Journal of Physical Chemistry B, Jahrgang 110, Nr. 11, 01.03.2006, S. 5279-5285.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Large ground-state and excited-state crystal field splitting of 8-fold-coordinate Cm3+ in [Y(H2O)8]Cl 3·15-crown-5
AU - Lindqvist-Reis, Patric
AU - Walther, Clemens
AU - Klenze, Reinhardt
AU - Eichhöfer, Andreas
AU - Fanghänel, Thomas
PY - 2006/3/1
Y1 - 2006/3/1
N2 - The optical spectra of Cm3+ incorporated into the crystalline host structure of [Y(H2O)8]Cl3·15-crown- 5 (1) is investigated by using laser spectroscopic methods at temperatures between 20 and 293 K. The coordination geometry of the [Y(H2O) 8]3+ entity in 1 is a distorted bicapped trigonal prism with ∼C2 point symmetry, as confirmed by single-crystal X-ray diffraction at 200 K. The crystal-field splitting of the 8S' 7/2 ground state and the 6D'7/2 and 6F5/2 excited states of the hydrated Cm3+ ion are measured by high-resolution fluorescence emission and excitation spectroscopy at various temperatures. The transitions between the ground state and the respective lowest crystal-field levels of the excited states exhibit narrow fluorescence lines, resolving the four crystal-field levels of the ground state as sharp, well-resolved lines at about 0, 10, 19, and 35 cm-1. The total splittings of the 6D'7/2 and 6P'5/2 states are 670 and 170 cm-1, respectively. Thermal population of the ground-state crystal-field levels is observed and quantified in the excitation spectra in the temperature range of 20-70 K. All spectroscopic results are consistent with the presence of one unique [Cm(H2O)8]3+ site. The ground-state splitting of Cm3+ in 1, 35 cm-1, is comparable to that of Cm3+ in solid ThO2, 36 cm-1, which shows the strongest crystal field for Cm3+ reported so far. For this reason the present results are different than the findings for Ln3+ aqua ions, which show rather weak crystal field strengths.
AB - The optical spectra of Cm3+ incorporated into the crystalline host structure of [Y(H2O)8]Cl3·15-crown- 5 (1) is investigated by using laser spectroscopic methods at temperatures between 20 and 293 K. The coordination geometry of the [Y(H2O) 8]3+ entity in 1 is a distorted bicapped trigonal prism with ∼C2 point symmetry, as confirmed by single-crystal X-ray diffraction at 200 K. The crystal-field splitting of the 8S' 7/2 ground state and the 6D'7/2 and 6F5/2 excited states of the hydrated Cm3+ ion are measured by high-resolution fluorescence emission and excitation spectroscopy at various temperatures. The transitions between the ground state and the respective lowest crystal-field levels of the excited states exhibit narrow fluorescence lines, resolving the four crystal-field levels of the ground state as sharp, well-resolved lines at about 0, 10, 19, and 35 cm-1. The total splittings of the 6D'7/2 and 6P'5/2 states are 670 and 170 cm-1, respectively. Thermal population of the ground-state crystal-field levels is observed and quantified in the excitation spectra in the temperature range of 20-70 K. All spectroscopic results are consistent with the presence of one unique [Cm(H2O)8]3+ site. The ground-state splitting of Cm3+ in 1, 35 cm-1, is comparable to that of Cm3+ in solid ThO2, 36 cm-1, which shows the strongest crystal field for Cm3+ reported so far. For this reason the present results are different than the findings for Ln3+ aqua ions, which show rather weak crystal field strengths.
UR - http://www.scopus.com/inward/record.url?scp=33645772633&partnerID=8YFLogxK
U2 - 10.1021/jp0574100
DO - 10.1021/jp0574100
M3 - Article
AN - SCOPUS:33645772633
VL - 110
SP - 5279
EP - 5285
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 11
ER -