Crystal-Field Spectra of <i>d</i>3,7 Ions. III. Spectrum of Cr3+ in Various Octahedral Crystal Fields

Wood, D. L.; Ferguson, J.; Knox, Kerro; Dillon, J. F.

doi:10.1063/1.1734388

Cited by 259 publications

(75 citation statements)

References 17 publications

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“…(ii) in the main bands, for which we confirm the absolute value of ,u and the general shape obtained in [ 5 ] , new structures were found. The oscillator strength is noticeably temperature dependent.…”

Section: The Crystal Field Band Regionsupporting

confidence: 87%

“…We realize that a value of x 160 cm-1 for the splitting of the 2E level is too large but if one takes into account the considerable hybridization of 4T, crystal field bands ; room temperature was obtained; and 4T, with 2E (Wood et al. [5] propose 16O/,) and makes detailed calculations following Sugano and Tanabe [14], better agreement may be reached.…”

Section: The Crystal Field Band Regionmentioning

confidence: 99%

“…Until recently [6] the studies of the intrinsic optical properties were limited to the so-called "crystal field l) A preliminary report of this work has been given a t the "International Symposium on Anisotropy in Layer Structures" Taormina, Italy, September 1968. bands", produced by the d-d dipole-forbidden intraconfigurational transitions of the chromium ion [5]. Various sharp peaks present in the paramagnetic [5] and ferromagnetic [l] phases and the main broad bands were attributed to the spin-forbidden quartet-to-doublet transitions and to the spin allowed quartetto-quartet transitions, respectively. I n particular the latter bands were assigned to transitions 4A2 --f 4T2 and 4A, --f 4T, in the order of increasing energy [ 5 ] .…”

Section: Introductionmentioning

confidence: 99%

“…Various sharp peaks present in the paramagnetic [5] and ferromagnetic [l] phases and the main broad bands were attributed to the spin-forbidden quartet-to-doublet transitions and to the spin allowed quartetto-quartet transitions, respectively. I n particular the latter bands were assigned to transitions 4A2 --f 4T2 and 4A, --f 4T, in the order of increasing energy [ 5 ] .…”

Section: Introductionmentioning

confidence: 99%

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Intrinsic Optical Properties of CrCl₃

Pollini

Spinolo

1970

Physica Status Solidi (b)

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The intrinsic optical absorption spectrum of CrCl, has been investigated in the 0.6 t o 6 eV region at temperatures from 80 to 300 OK. A careful analysis of the crystal field bands in the 0.6 to 3 eV region has revealed some structures and details, such as an Urbach's rule edge, not previously reported. The optical anisotropy of CrC1, was also studied over the same spectral range. I n the region between 3 and 8 eV reflectivity spectra were also obtained. The refractive index of CrC1, has been determined on evaporated films from 1000 to 380 nm [n(500 nm) = 1.85 f 0.11. The spectral distribution of photocurrent at % 80 "K was measured and showed weak peaks associated with the main crystal field bands and a sharp increase at shorter wavelengths ; maximum photoconductivity yield was reached a t (3.2 0.2) eV. The data on the crystal field bands are discussed and some new structures are assigned to specific electronic transitions. Account is taken of the spin-orbit interaction among the various multiplets and the trigonal distortion of the octahedral symmetry of the Cr3+ environment. A discussion of the optical and photoconductivity data in the 3 to 8 eV region is given and alternative explanations of the absorption edge a t 3.2 eV are proposed. faibles maxima associi?s aux bandes principales de la rbgion visible du spectre e t une forte absorption aux plus courtes longueurs d'onde; le maximum de photocourant a Btb trouvb (3,2 f 0,2) eV. Les rbsultats obtenus dans la region spectrale 0,6 It 3 eV ont btk discutbs, considbrant aussi le couplage spin-orbite e t la distortion trigonale de l'entourage de l'ion Cr3+. Une discussion des donnhes optiques et photoblectriques entre 3 e t 8 eV a 6th faite rt des explications alternatives pour le bord d'absorption B 3,2 eV ont btt5 suggbrkes.

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Section: The Crystal Field Band Regionsupporting

confidence: 87%

Section: The Crystal Field Band Regionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Intrinsic Optical Properties of CrCl₃

Pollini

Spinolo

1970

Physica Status Solidi (b)

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“…25,26 By contrast, many other authors have suggested that unpaired electrons are not fully localized on the CrO 6 9− complex as they are also present in the second and further coordination spheres, which are not the same in ruby and emerald. 2,[27][28][29] According to this view the flow of electronic charge outside the CrO 6 9− complex would be responsible for the different 10Dq value exhibited by gemstones like ruby and emerald.…”

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confidence: 99%

Internal electric fields and color shift in Cr3+-based gemstones

et al. 2012

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Seeking to better understand the origin of the different colors of emerald and ruby, both ab initio periodic and cluster calculations have been carried out. impurities along the series of ionic oxides can be understood merely through the CrO 6 9− unit but subject to the electric field due to the rest of the lattice ions. As a salient feature it is proved that changes in electronic density and covalency due to the internal field are not the cause of the color shift. Therefore, the red color of ruby is not due to the polarization of the electronic cloud around chromium as a result of the C 3 local symmetry. The present study also demonstrates that the variation of the ligand field splitting parameter, 10Dq, induced by the internal electric field comes mainly from the contributions of first shells of ions around the CrO 6 9− unit. As a consequence, 10Dq in emerald is not influenced by the internal field, as the contribution from Be 2+ first neighbors is practically compensated by that of Si 4+ second neighbors. In contrast, in ruby the t 2g levels are shifted by the internal field 0.24 eV more than the e g ones, so explaining the color shift in this gemstone in comparison with emerald. This result is shown to arise partially from the asymmetric form of the internal electrostatic potential along the C 3 axis in Al 2 O 3 .

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