The 6<i>d</i>→5<i>f</i> fluorescence spectra of PaCl2−6 in a Cs2ZrCl6 crystal

Piehler, D.; Edelstein, N.

doi:10.1063/1.459984

Cited by 33 publications

(29 citation statements)

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“…The solutions of the above Hamiltonian for a 4f 1 or a 5d 1 electron configuration are well known and will not be repeated. 28 The emission and absorption transitions reported in this paper between the 4f 1 and Cs 2 NaCeCl 6 have been reported and are dominated by magnetic dipole transitions. 31 Although the former is cubic at low temperatures, the latter undergoes a phase transition at 178 K. 10,[32][33][34] The infrared absorption spectra were reinvestigated in this study and the derived energy levels are listed in …”

Section: Review Of Parametric Theorymentioning

confidence: 92%

“…The solutions of the above Hamiltonian for a 4f 1 or a 5d 1 electron configuration are well known and will not be repeated. 28 The emission and absorption transitions reported in this paper between the 4f 1 and 5d 1 configurations are allowed electric dipole transitions that originate or terminate either in crystal field states of Γ 7u , Γ 8u , or Γ 6u symmetry for the 4f 1 configuration or Γ 8g or Γ 7g for the 5d 1 configuration. The electric dipole operator transforms as Γ 4u .…”

Section: Review Of Parametric Theorymentioning

confidence: 99%

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Absorption and Emission Spectra of Ce³⁺ in Elpasolite Lattices

et al. 2003

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The experimental determination of the electronic energy levels for Ce 3+ in some chloro-elpasolite hosts for both the ground 4f 1 and the excited 5d 1 configurations are described. High resolution f -f absorption and f -2 T 2g d absorption and emission spectra have been recorded at low temperatures for Ce 3+ diluted into various hexachloroelpasolite lattices. A fluorescence spectrum at ~ 50,000 cm -1 is tentatively assigned to the emission from the highest 5d crystal field level , 2 E g , of a Ce 3+ impurity in Cs 2 NaErCl 6 , enabling the values of all the energy levels of both the 4f 1 and 5d 1 configurations to be given for 2 Ce 3+ in elpasolite hosts. Vibronic structure superimposed on the electronic transitions is analyzed in terms of a simple configurational coordinate model involving the ground and excited configurations. It is found that the difference in the Ce-Cl bondlength between the 4f 1 and 5d 1 configurations is ~0.04Å. Ab initio model potential calculations on the (CeCl 6 ) 3-cluster embedded in a reliable representation of the Cs 2 NaYCl 6 host support these conclusions. IntroductionAt the beginning of the 4f and the 5f transition series, the f and d electronic configurations of the di-, tri-, and tetravalent free ions are very close in energy. 1,2 This is also true for these ions in compounds. For example, the lowest energy configuration for the Ce 2+ free ion is [Xe core]4f 2 with the beginning of the opposite parity 4f5d configuration at 3277 cm -1 . However in a CaF 2 host the ground configuration is [Xe core]4f5d. 3 The Ce 3+ free ion has a 4f 1 ground configuration with the lowest 5d state at 49737 cm -1 . 1 When this ion is placed in a crystal the lowest 4f to 5d electric dipole allowed transition has been reported to be in the range of 20,000 to 40,000 cm -1 depending on the particular compound or matrix investigated. 4 Similarly, for the actinide or 5f series, the lowest 5f -6d transition for the Pa 4+ ion diluted in Cs 2 ZrCl 6 is at 20,000 cm -1 , but the free ion separation between ground 5f level and the first 6d level is ~ 50,000 cm -1 . 5 In the few structurally characterized Th 3+ organometallic compounds the 6d 1 configuration has been found to be the ground configuration, 6,7 but the ground term is from the 5f configuration and the first 6d level is 10,000 cm -1 higher in the Th 3+ free ion.The U 3+ ion in the LaCl 3 host has the first 5f 3 to 5f 2 6d 1 transition at approximately 22,000 cm -1 although in the U 3+ /RbY 2 Cl 7 system this transition is found at ~ 14,000 cm -1 . 8 Thus, as the degree of ionization increases and/or the atomic number is increased (for both the lanthanide and the actinide series) the f n configuration becomes increasingly stabilized so that the interconfigurational transitions are not observed in the visible or near ultraviolet region. Only at the beginning of both the lanthanide and actinide series is it possible to observe these two electronic configurations in this energy range. 3For the lanthanide series the Ce 3+ ion has been extensivel...

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Section: Review Of Parametric Theorymentioning

confidence: 92%

“…The solutions of the above Hamiltonian for a 4f 1 or a 5d 1 electron configuration are well known and will not be repeated. 28 The emission and absorption transitions reported in this paper between the 4f 1 and 5d 1 configurations are allowed electric dipole transitions that originate or terminate either in crystal field states of Γ 7u , Γ 8u , or Γ 6u symmetry for the 4f 1 configuration or Γ 8g or Γ 7g for the 5d 1 configuration. The electric dipole operator transforms as Γ 4u .…”

Section: Review Of Parametric Theorymentioning

confidence: 99%

Absorption and Emission Spectra of Ce³⁺ in Elpasolite Lattices

et al. 2003

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“…The final results are in excellent agreement with the detailed experimental measurements of Refs. 1 and 2, not only in their absolute values but also in their small reduction from the 5 f 1 states ͑all of them essentially equal, 310 cm Ϫ1 ) to the 6d(t 2g ) 1 states ͓302 cm Ϫ1 in ⌫ 8g ͓5/2( 2 D)͔͔. According to our results, the 6d(e g ) 1 state (⌫ 8g ͓3/2( 2 D)͔) shows a significantly smaller force constant ( a 1g ϭ271 cm Ϫ1 ), which has not yet been measured.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4] Contrary to the case of 5 f →5 f transitions, they are often not well understood. 3,4 In effect, the 5 f →5 f transitions are identified with the help of the crystal field theory ͑CFT͒.…”

Section: Introductionmentioning

confidence: 99%

“…We optimized the Pa-Cl distance of the (PaCl 6 ) 2Ϫ unit under O h symmetry, R e , in all the states of main configuration 5 f 1 and 6d 1 , and we calculated the breathing mode vibrational frequencies, a 1g . From the energy curves, we calculated the minimum to minimum transition energy, T e , that can be directly compared with the experimental zero-phonon or 0-0 transition energies because the vibrational frequencies of all the states are very similar.…”

Section: àmentioning

confidence: 99%

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Structure and spectroscopy of Pa4+ defects in Cs2ZrCl6. An ab initio theoretical study

Seijo

Barandiarán

2001

The Journal of Chemical Physics

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In this paper we present the results of spin-orbit relativistic ab initio model potential embedded cluster calculations on (PaCl 6 ) 2Ϫ embedded in a reliable representation of the Cs 2 ZrCl 6 host. Totally symmetric local distortions and vibrational frequencies are calculated for all the states of the 5 f 1 and 6d 1 manifolds, as well as the corresponding 5 f ↔6d transition energies and the shape of the 5 f (⌫ 8u )←6d(⌫ 8g ) fluorescence band. An excellent overall agreement with available experimental data is observed which allows us to conclude that the quality of the spin-orbit operators used is very high for actinide elements, as was already known for transition metal and lanthanide elements. Furthermore, it is concluded that the structural and spectroscopic information produced here is very reliable and that the 6d(⌫ 8g Ј ) state is around 10 000 cm Ϫ1 higher in energy than it was thought; our calculations suggest a value of 30 000 cm Ϫ1 for the 10Dq parameter of Pa 4ϩ in Cs 2 ZrCl 6 , which would be compatible with the lower limit of 20 000 cm Ϫ1 accepted for Ce 3ϩ in Cs 2 NaYCl 6 .

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