Paramagnetic Resonance Absorption in Titanium Caesium Alum at Low Temperatures

Bijl, D.

doi:10.1088/0370-1298/63/4/110

Cited by 31 publications

(10 citation statements)

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“…where ⌬ is the cubic ligand field splitting of the t 2 and e orbitals, , and k are the basic one-electron trigonal field, spin-orbit coupling and orbital reduction parameters for t 2 orbitals, respectively, and Ј, Ј and kЈ are the corresponding set connecting t 2 …”

Section: T 2 E Coupling In Trigonal Symmetrymentioning

confidence: 99%

“…The direct product t 2 ϫt 2 ϭa 1 ϩeϩ[t 1 ]ϩt 2 shows that all the low symmetry distortions of the 2 T 2 multiplet can be described by five real cubic tensors V(⌫M ) ͓see Eq. ͑8͔͒.…”

Section: T Coupling and Low Symmetry Potentialsmentioning

confidence: 99%

“…1 The paramagnetism and, in particular, the magnetic g values of CsTiS have been an unresolved problem for more than forty years. [2][3][4][5][6][7] Unlike the electron paramagnetic resonance ͑EPR͒ of Ti 3ϩ doped into an ␣ alum such as RbAlS 8 where twelve magnetically inequivalent sites were observed and correspond to one chemical species with rhombic symmetry, the single crystal EPR of CsTiS indicated one chemical species of trigonal symmetry with g ʈ ϭ1. 25 and g Ќ ϭ1.14.…”

Section: Introductionmentioning

confidence: 99%

“…3 If the trigonal field that lifts the degeneracy of the t 2 d-orbitals of the Ti 3ϩ ions has a positive sign, ϭE(t 2 x 0 )ϪE(t 2 x Ϯ ) is greater than zero, then the ground Kramers doublet in S 6 symmetry has the symmetry classification (t 2 x Ϯ 1 ) 2 T 2 (2⌫ 6 ) where we use the complex trigonal basis for t 2 orbitals 9 and the double group notation of Koster et al 10 The 2⌫ 6 doublet transforms as the M J ϭϮ 11 The g ʈ value differs appreciably from the prediction of the static ligand field model that gives to first order, g ʈ (2⌫ 6 )ϭ2Ϫ2K z Ϸ0.5, where K z is the effective orbital reduction factor for the (t 2 1 ) 2 T 2 multiplet. The explanation of this discrepancy as well as accounting for the energies of the low-lying vibronic states at 38 cm Ϫ1 and 108 cm Ϫ1 was a major success for Ham's effective Hamiltonian treatment of the 2 T 2 e Jahn-Teller problem. 11,12 Since for positive the ground state of the Ti 3ϩ ion will always remain 2⌫ 6 with g Ќ ϭ0, the early attempts to account for g Ќ ϭ1.14 in CsTiS employed a negative value of .…”

Section: Introductionmentioning

confidence: 99%

“…Since the trigonal splitting of the t 2 orbitals ͑see Sec. IV͒ is much greater than the spin-orbit coupling of Ti 3ϩ or the JahnTeller coupling, it is the trigonal field which tends to break 2 T 2 ( 2 Eϩ 2 A) e coupling into 2 E e and 2 A, and quenches the pseudo-Jahn-Teller coupling between 2 E and the higher lying 2 A, where E and A are the trigonal orbital species of the T 2 parent. Figure 1͑b͒ shows a schematic hierarchy of perturbations to the d electronic levels of a Ti͑III͒ complex.…”

Section: Introductionmentioning

confidence: 99%

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Paramagnetism of caesium titanium alum

Dubicki¹,

Riley²

1997

The Journal of Chemical Physics

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Articles you may be interested in Ab initio study of dynamical E × e Jahn-Teller and spin-orbit coupling effects in the transition-metal trifluorides TiF3, CrF3, and NiF3 J. Chem. Phys. 136, 084308 (2012) Caesium titanium alum, CsTi͑SO 4 ͒ 2 •12H 2 O, is a ␤ alum and exhibits a large trigonal field and a dynamic Jahn-Teller effect. Exact calculations of the linear 2 T 2 e Jahn-Teller coupling show that in the strict S 6 site symmetry the ground multiplet consists of a Kramers doublet 2⌫ 6 with magnetic splitting factors g ʈ ϭ1.1 and g Ќ ϭ0, a ⌫ 4 ⌫ 5 doublet at ϳ60 cm Ϫ1 with g ʈ ϭ2.51 and g Ќ ϭ0.06 and another ⌫ 4 ⌫ 5 doublet at ϳ270 cm Ϫ1 with g ʈ ϭ1.67 and g Ќ ϭ1.83. The controversial g values observed below 4.2 K, g ʈ ϭ1.25 and g Ќ ϭ1.14, are shown to arise from low symmetry distortions. These distortions couple the vibronic levels and induce into the ground state the off-diagonal axial Zeeman interaction that exists between the first excited and the ground vibronic levels. © 1997 American Institute of Physics. ͓S0021-9606͑97͒01804-7͔

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Section: T 2 E Coupling In Trigonal Symmetrymentioning

confidence: 99%

Section: T Coupling and Low Symmetry Potentialsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Paramagnetism of caesium titanium alum

Dubicki¹,

Riley²

1997

The Journal of Chemical Physics

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The Jahn–Teller Effect of the Ti^III Ion in Aqueous Solution: Extended Ab Initio QM/MM Molecular Dynamics Simulations

2004

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Combined ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulations, including only the first and the first and second hydration shells in the QM region, were performed for TiIII in aqueous solution. The hydration structure of TiIII is discussed in terms of radial distribution functions, coordination-number distributions and several angle distributions. Dynamical properties, such as librational and vibrational motions and TiIII-O vibrations, were evaluated. A fast dynamical Jahn-Teller effect of TiIII(aq) was observed in the QM/MM simulations, in particular when the second hydration shell was included into the QM region. The results justify the computational effort required for the inclusion of the second hydration shell into the QM region and show the importance of this effort for obtaining accurate hydration-shell geometries, dynamical properties, and details of the Jahn-Teller effect.

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