Magnetic susceptibilities of trivalent lanthanide ions in an octahedral environment

Hoehn, M.V.; Karraker, D.G.

doi:10.1063/1.1681053

Cited by 58 publications

(17 citation statements)

References 12 publications

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“…The transition at 55 cm -1 is Alg-->TI~ and hence cannot be detected in the Raman experiment. A level between 40 and 50 cm -1 was found earlier from paramagnetic susceptibility data [20]. A reinterpretation of that data [21] reported a Tlg level at 49 cm -1 and a T2o level at 127 cm -1, again in essential agreement with the present results.…”

Section: Discussionsupporting

confidence: 92%

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

1979

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Section: Discussionsupporting

confidence: 92%

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

1979

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“…Utilizing these parameters and those in tables 1 and 2, we calculate B0(k)(chg) (k=4 and 6) and B0(k)(pol) (k=4 and 6) according to (2) and (3) [22] for Eu 3+ are in error due to the use of Eu 2+ radial integrals rather than Eu ~+ radial integrals. The so-called empirical values of B0 (4) and B0 (6) obtained from crystal field analyses of the optical absorption and emission spectra of several Cs2NaLnCI n systems are listed in table 5.…”

Section: Throrymentioning

confidence: 99%

“…The spectroscopic and magnetic properties of cubic Cs~NaLnC1 e elpasolite systems have been the subject of numerous studies reported over the past 10 years [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. At room temperature, the crystalline form of these compounds is cubic (space group Fm3m} with the lanthanide ions situated at sites with exact octahedral (Oh) symmetry [21].…”

Section: Introductionmentioning

confidence: 99%

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The lanthanide crystal field in cubic Cs₂NaLnCl₆elpasolites

et al. 1980

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The octahedral lanthanide crystal field is calculated for trivalent lanthanide ions (Ln 3+) in the cubic C%NaLnC16 elpasolite structure. These calculations are based on a model which includes two types of Ln3 § interactions: multipole(Lna+)-point charge(ligand) and charge(Lna+)-induced dipole(ligand). The latter interaction mechanism involving ligand dipolar polarization is shown to make the dominant contributions (~ 80-85 per cent of the total) to the B0 t4) and B0 cG) octahedral crystal field coefficients. The calculated values of B0 o) are in good quantitative agreement with empirically determined values, while the calculated B0(6) values are found to be about 2-4 times too small in magnitude. The trends of both B0t4)(calc) and B0<6)(calc) across the lanthanide series are in excellent qualitative agreement with experiment. It is found that the six chloride ions in the first coordination sphere of a Ln 3+ ion contribute > 95 per cent of the calculated Bo C~l and B0 c6) values. The ligand parameters included in the crystal field model (charge, dipolar polarizability, and positional coordinates) are exactly the same as those used in the extant f-[ intensity models for the Cs2NaLnC16 elpasolite systems.

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“…These results have been used extensively in a variety of investigations [84][85][86][87] on lanthanide ions in the elpasolite lattice, which is of the formula A2BRX 6 , with A and B alkali metals, R the lanthanide and X either fluoride or, more commonly, chloride. The rare earth ion resides at a site of cubic symmetry in these compounds.…”

Section: Some Other Systemsmentioning

confidence: 99%

The Rare Earths or Lanthanides

Carlin

1986

Magnetochemistry

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The paramagnetic properties of the rare earth ions have been investigated so extensively that a book could be written on the subject, never mind a chapter. This is due in large part to the many studies ofthe EPR spectra of the lanthanides when doped into diamagnetic hosts, and the attendant theoretical development in terms of crystal field theory. Many of the current ideas in magnetism have followed from such studies, especially with regard to relaxation phenomena.Relatively few coordination compounds of the lanthanides have been studied in detail. Superexchange is relatively unimportant, and dipole-dipole interactions therefore tend to dominate the magnetic ordering phenomena; this is enhanced by both the relatively large spin and g-values of many ofthe lanthanides. The compounds which order do so largely at temperatures of 4 K and below as a result. These effects are enhanced by the high coordination number of most rare earth compounds, which works to reduce the strength of any superexchange paths. Also, as a result, there appear to be no lower-dimensional rare earth compounds, at least in the sense described in Chap. 7.It is difficult to generalize about each ion, since the crystal field splitting of any ion, though small, can change from one system to another.The chemistry of the lanthanides has been reviewed [1-3]. The distinguishing features for our purposes are:a) The metal ions are found primarily in the trivalent state. b) High coordination numbers (eight appears to be the commonest) and a variety of geometries are found. Six-coordination and lower are rare. Several typical coordination polyhedra are illustrated in Fig. 9.1. c) Oxygen and nitrogen are the favored donor atoms, but a number of halides have also been studied. d) Spin-orbit coupling is important, the more so energetically than crystal field splittings, and increases with atomic number. This is summarized in Table 9.1. The letter " is once again used as the total angular momentum quantum number.e) The magnetic properties are determined by the 4f electrons, which are wellshielded by the occupied outer shells of 5s and 5p electrons. The 4f electrons are littleinvolved with chemical bonding, which is why superexchange is relatively unimportant. This is well-illustrated in Fig. 9.2, which shows the radial extension of the wave functions [6]. The interactions which dominate the cooperative phenomena with rare earth compounds are dipolar in nature. This is because of the important orbital contributions to the magnetic moment. Thus, since dipole-dipole interactions are long-R. L. Carlin, Magnetochemistry

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Magnetic susceptibilities of trivalent lanthanide ions in an octahedral environment

Cited by 58 publications

References 12 publications

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

The lanthanide crystal field in cubic Cs₂NaLnCl₆elpasolites

The Rare Earths or Lanthanides

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Magnetic susceptibilities of trivalent lanthanide ions in an octahedral environment

Cited by 58 publications

References 12 publications

The absorption and magnetic circular dichroism spectra of Cs2NaTmCl6

The absorption and magnetic circular dichroism spectra of Cs2NaTmCl6

The lanthanide crystal field in cubic Cs2NaLnCl6elpasolites

The Rare Earths or Lanthanides

Contact Info

Product

Resources

About

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

The absorption and magnetic circular dichroism spectra of Cs₂NaTmCl₆

The lanthanide crystal field in cubic Cs₂NaLnCl₆elpasolites