Selection rules for the electronic Raman effect

Kiel, A.; Porto, S. P. S.

doi:10.1016/0022-2852(69)90011-3

Cited by 43 publications

(16 citation statements)

References 6 publications

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“…A A-Übergänge sind polarisiert (p <3/4), A A-und A A-Übergänge sind depolarisiert (p = 3/4) bzw. vor allem unter RR-Bedingungen anomal polarisiert (p > 3/4) [32]. …”

unclassified

Darstellung und spektroskopische Charakterisierung von Tetrahalogenooxalato-Osmaten(IY) / Preparation and Spectroseopical Characterisation of Tetrahalooxalato-osmates(IV)

Homborg¹,

Preetz²,

Barka³

et al. 1980

Zeitschrift Für Naturforschung B

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Reaction of [OsX6]2- (X = CI, Br, I) with oxalic acid in water gives the very stable and deeply coloured new complexes [OsX40x]2- which can be precipitated as alkali or tetraalkylammonium salts. The salts with long-chain alkylammonium ions are soluble in all common no polar solvents. The IR and Ra spectra and the depolarization ratios are consistent with the local C2v-symmetry. The coupling between the vibrations of coordinated oxalate and with the skeletal [OsX4O2]-modes is apparently small. The optical spectra have been studied at low temperature (10 K). Analogous to [OsXe]2- the very intense absorptions in the UV and VIS are assigned to the electric dipole allowed electron transfer from "(π+σ)t1u, πt2U(γ7), πt2u(γ8) and (σ+π)t1u" to "dt2g". By the descent in symmetry each of these transitions is further split in three components (A1, B1, B2) corresponding to the three different groups of ligands, X2tr-, X2c. and ox. The distinction between the X2tr. →Os and X2c- → Os is caused by a static trans-effect and depends on the difference of the optical electronegativities induced by ox. This splitting is not observed for [OsCl4ox]2- but is about 900 cm-1 for [OsBr4ox]2- and 1200 cm-1 for [OsI4ox]2-. The well defined bands in the NIR and VIS are assigned to the intraconfigurational d-dtransitions between the spin-orbit components in the octahedral doublegroup Oh* splitted by the lower C2v-symmetry. Some of the zero-phonon transitions within the split of the 3Tlg, Oh-groundstate exhibit extremely high intensities (e~2500 cm2/mmol). The assignment of these transitions is improved by the electronic Ra spectra. The finestructure of some of the d-d-transitions originates from coupling with A1 vibrational modes especially with νs(C-O).

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“…A A-Übergänge sind polarisiert (p <3/4), A A-und A A-Übergänge sind depolarisiert (p = 3/4) bzw. vor allem unter RR-Bedingungen anomal polarisiert (p > 3/4) [32]. …”

unclassified

Darstellung und spektroskopische Charakterisierung von Tetrahalogenooxalato-Osmaten(IY) / Preparation and Spectroseopical Characterisation of Tetrahalooxalato-osmates(IV)

Homborg¹,

Preetz²,

Barka³

et al. 1980

Zeitschrift Für Naturforschung B

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“…The appropriateness of this attribution may once again be discussed based on the polarization dependence of the new features, which is similar to that of V1. In the CF picture the hexagonal symmetry of the Ce site in CePt 5 leads to a splitting of the j = 5/2 multiplet into three Kramers doublets of pure m j = ±1/2, ±3/2, and ±5/2 character, which belong to the double group representations Γ − 7 , Γ − 9 , and Γ − 8 [20,31]. Since the quadrupole selection rules for CE Raman transition in the present geometry require ∆m j = ±2, only the transitions involving the m j = ±1/2 doublet are symmetry allowed, i.e.…”

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confidence: 99%

Study of crystal-field splitting in ultrathinCePt5films by Raman spectroscopy

et al. 2017

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Low-temperature electronic properties of rare-earth intermetallics are substantially influenced by the symmetry and magnitude of the crystal electric field. The direct spectroscopic analysis of crystal field splitting can be challenging, especially in low-dimensional systems, because it requires both high spectral resolution and pronounced sensitivity. We demonstrate the eligibility of electronic Raman spectroscopy for this purpose by the direct determination of the 4f level splitting in ultrathin ordered CePt5 films down to 1.7 nm thickness on Pt(111). Crystal field excitations of Ce 4f electrons give rise to Raman peaks with energy shifts up to ≈ 25 meV. Three distinct peaks occur which we attribute to inequivalent Ce sites, located (i) at the interface to the substrate, (ii) next to the Pt-terminated surface, and (iii) in the CePt5 layers in between. The well-resolved Raman signatures allow us to identify a reduced crystal field splitting at the interface and an enhancement at the surface, highlighting its strong dependence on the local atomic environment.

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“…We will deal also with the case of the TbVO 4 crystals here. The selection rules for D 2d site symmetry 19 allow electron dipole transitions between levels of Tb 3C in accordance with Table 1. Let us consider the Raman scattering connected with electronic transitions from or to low-lying A 1 , B 1 levels.…”

Section: Electronic Raman Scatteringmentioning

confidence: 89%

Specific features of Raman scattering in crystals with a cooperative Jahn-Teller effect

Stasyuk¹,

Ivankiv²

1999

J. Raman Spectrosc.

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A microscopic approach which permits Raman scattering in a dielectric crystal is presented to be described in a uniform way. Additional features of the temperature dependences in the spectrum of Raman scattering of phonons are obtained, arising owing to presence of low-lying nearly degenerated electronic levels typically occurring in crystals with Jahn-Teller phase transitions. The changes in the populations of these levels may influence the temperature dependences in Raman spectra. The theory describes also the electronic Raman effect in these crystals.

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Selection rules for the electronic Raman effect

Cited by 43 publications

References 6 publications

Darstellung und spektroskopische Charakterisierung von Tetrahalogenooxalato-Osmaten(IY) / Preparation and Spectroseopical Characterisation of Tetrahalooxalato-osmates(IV)

Darstellung und spektroskopische Charakterisierung von Tetrahalogenooxalato-Osmaten(IY) / Preparation and Spectroseopical Characterisation of Tetrahalooxalato-osmates(IV)

Study of crystal-field splitting in ultrathinCePt5films by Raman spectroscopy

Specific features of Raman scattering in crystals with a cooperative Jahn-Teller effect

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