Jahn-Teller distortion in tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]manganese(III) isomers: An X-ray and computational study

We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys. Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation. The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller effect in benzene cation.

Download Full-text

Influence of static Jahn-Teller distortion on the magnetic excitation spectrum ofPrO2: A synchrotron x-ray and neutron inelastic scattering study

Physical Review B ◽

10.1103/physrevb.76.134419 ◽

2007 ◽

Vol 76 (13) ◽

Cited By ~ 13

Author(s):

C. H. Webster ◽

L. M. Helme ◽

A. T. Boothroyd ◽

D. F. McMorrow ◽

S. B. Wilkins ◽

...

Keyword(s):

Inelastic Scattering ◽

Excitation Spectrum ◽

Magnetic Excitation ◽

Teller Distortion ◽

Neutron Inelastic Scattering ◽

X Ray ◽

Jahn Teller ◽

Scattering Study ◽

Jahn Teller Distortion

Download Full-text

Die Jahn-Teller-Verzerrung in den Kristallstrukturen der Dinatrium-Tetrafluorometallate Na2CuF4 und Na2CrF4 / The Jahn-Teller Distortion in the Crystal Structures of the Disodium-Tetrafluorometallates Na2CuF4 and Na2CrF4

Zeitschrift für Naturforschung B ◽

10.1515/znb-1989-0701 ◽

1989 ◽

Vol 44 (7) ◽

pp. 715-720 ◽

Cited By ~ 8

Author(s):

Dietrich Babel ◽

Michael Otto

Keyword(s):

Crystal Structures ◽

Chain Structure ◽

Teller Distortion ◽

Space Group ◽

X Ray ◽

Edge Sharing Octahedra ◽

Jahn Teller ◽

A Chain ◽

Jahn Teller Distortion ◽

Ray Methods

The crystal structures of the isotypic monoclinic fluorides Na2CuF4 (a = 326.7(1), b = 937.0(2), c = 561.2(1) pm, β = 92.49(1)°; V = 171.63 x10-30 m3) and Na2CrF4 (a = 334.8(1), b = 954.9(2), c = 566.5(3) pm, β = 92.85(3)°; V = 180.89 × 10-30 m3) have been redetermined by single crystal X-ray methods. The compounds are Jahn-Teller distorted variants of the orthorhombic Sr2PbO4type (space group Pbam) and crystallize with Z = 2 in space group P21/c, a subgroup of Pbam. They form a chain structure of edge-sharing octahedra which are strongly elongated. The following distances were obtained: Cu-F = 190.4/193.8/235,7(2) pm and Cr-F = 199.1/199.7/241.7(4) pm. The geometry is compared to that of the corresponding distorted rutile type difluorides; relations to further compounds are discussed.

Download Full-text

An investigation of the electron density of a Jahn–Teller-distorted CrIIcation: the crystal structure and charge density of hexakis(acetonitrile-κN)chromium(II) bis(tetraphenylborate) acetonitrile disolvate

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615015739 ◽

2015 ◽

Vol 71 (11) ◽

pp. 936-943 ◽

Cited By ~ 5

Author(s):

Arumugam Thangavel ◽

Marika Wieliczko ◽

Christopher Scarborough ◽

Birger Dittrich ◽

John Bacsa

Keyword(s):

Crystal Structure ◽

Electron Density ◽

Topological Analysis ◽

Electronic Density ◽

Teller Distortion ◽

X Ray ◽

Structure Factors ◽

Jahn Teller ◽

Jahn Teller Distortion ◽

Detailed Picture

In the crystal structure of the title homoleptic CrIIcomplex, [Cr(CH3CN)6](C24H20B)2·CH3CN, the [Cr(CH3CN)6]2+cation is a high-spind4complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single-crystal X-ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the CrIIcation away from idealized octahedral symmetry. The topological analysis of the asphericald-electron density about the CrIIcation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the CrIIcation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller-distorted six-coordinate complex.

Download Full-text

Evidence for a Jahn-Teller distortion of Cs2NaHoCl6 at 150 mK observed by X-ray diffractometry

Journal of Low Temperature Physics ◽

10.1007/bf00760807 ◽

1994 ◽

Vol 96 (1-2) ◽

pp. 47-59 ◽

Cited By ~ 4

Author(s):

Tetsuo Nakajima ◽

Haruhiko Suzuki

Keyword(s):

Teller Distortion ◽

X Ray ◽

Jahn Teller ◽

Jahn Teller Distortion

Download Full-text

X-ray diffraction measurement of the Jahn-Teller distortion in TmVO4

Solid State Communications ◽

10.1016/0038-1098(74)90023-4 ◽

1974 ◽

Vol 15 (1) ◽

pp. 101-104 ◽

Cited By ~ 25

Author(s):

Armin Segmüller ◽

R.L. Melcher ◽

H. Kinder

Keyword(s):

Diffraction Measurement ◽

X Ray Diffraction ◽

Teller Distortion ◽

X Ray ◽

Jahn Teller ◽

Jahn Teller Distortion

Download Full-text

5d STATES AND RESONANT X-RAY SCATTERING FROM CeB6

Surface Review and Letters ◽

10.1142/s0218625x02003524 ◽

2002 ◽

Vol 09 (02) ◽

pp. 1203-1207

Author(s):

TATSUYA NAGAO ◽

JUN-ICHI IGARASHI

Keyword(s):

Dominant Role ◽

Earth Metal ◽

Metal Compound ◽

Teller Distortion ◽

X Ray ◽

X Ray Scattering ◽

Jahn Teller ◽

Jahn Teller Distortion ◽

Good Agreement ◽

Ray Scattering

We study the origin of the resonant X-ray scattering (RXS) signal near the Ce L III absorption edge in the antiferroquadrupolar (AFQ) ordering phase of CeB 6. In this rare-earth metal compound, the intra-atomic Coulomb interaction plays a dominant role to give the large RXS intensities, which shows a sharp contrast with the Jahn–Teller distortion mechanism realized in the transition metal compound such as LaMnO 3. The temperature and magnetic field dependences show good agreement with the recent experiment, indicating that the RXS signal is a direct reflection of the AFQ order parameter.

Download Full-text