The vibrational spectrum of solid ferrocene by inelastic neutron scattering

Kemner, Ewout; Schepper, I. M. de; Kearley, Gordon J.; Jayasooriya, Upali A.

doi:10.1063/1.481731

Cited by 39 publications

(34 citation statements)

References 13 publications

(25 reference statements)

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“…Bei einer Messtemperatur von 50 K sind nicht nur der KFGrundzustand 1Γ 7 , sondern auch der ca. 50 cm −1 höher gelegene angeregte Zustand 1Γ 9 ausreichend thermisch populiert [32], so dass bei der beabsichtigten Zuordnung der beobachteten vibronischen Seitenbanden insgesamt sechs rein elektronische KF-Zustände berücksichtigt werden müssen (obwohl der 0-0-Absorptionsübergang 1Γ 7 ( 4 I 9/2 ) → 18Γ 7 ( 4 G 5/2 ) symmetrieverboten ist; siehe Tabelle 858, 1076 und 1373 cm −1 von den rein elektronischen hypersensitivenÜbergängen separiert sind [45] und gemäß unserer DFT-Rechnung an 2 mit C-C-Ring-Deformation oop , C-C-Ring- [47]) auf [46].…”

Section: Skelettschwingungenunclassified

Zur Elektronenstruktur metallorganischer Komplexe der ƒ -Elemente, 81. Berechnung der Normalschwingungen von La(η⁵-C₅H₅)₃(NCCH₃)₂ auf der Basis der Dichtefunktionaltheorie sowie vibronische Kopplungen und Auffindung weiterer rein elektronischer Absorptions- und Lumineszenzüberg¨ange bei [La(η⁵-C₅H₅)₃(NCCH₃)₂:Nd³⁺] / Electronic Structures of Organometallic Complexe

Amberger

Reddmann

2013

Zeitschrift Für Naturforschung B

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The planned model calculations of normal modes of pseudo-trigonal-bipyramidal LaCp 3 (NCCH 3 ) 2 (Cp = η 5 -C 5 H 5 − ) (1) adopting density functional theory (DFT), and using the molecular structure as suggested by X-ray investigations, did not converge. Alternatively, DFT calculations assuming molecular C 3h symmetry were performed. Unfortunately, these calculations did not reproduce the experimentally derived frequencies of the skeletal modes very well, including a wrong energetic sequence of the four previously unambiguously assigned (close lying) Raman-active ν(La-Cp) skeletal modes. The same presumably also holds for DFT calculations made for LaCp 3 ·NCCH 3 (2) and base-free LaCp 3 (3), assuming molecular C 3 and C 3h symmetry, respectively. In order to check whether the calculated incorrect sequence is produced by the five-membered Cp rings, a DFT calculation also has been performed for the hypothetical model complex [La(η 6 -C 6 H 6 ) 3 ] 3+ (4) of D 3 symmetry.A closer examination of the vibronic sidebands of the hypersensitive absorption transition 4 I 9/2 → 4 G 5/2 of [LaCp 3 (NCCH 3 ) 2 :Nd 3+ ] (5) showed that first of all, totally symmetric intraligand and not skeletal vibrations are coupling as it was the case for [LaCp 3 (NCCH 3 ) 2 :Ln 3+ ] (Ln = Pr, Sm). Applying this result to the vibronic sidebands of some purely electronic crystal field (CF) transitions, which are hampered by strong binary combination vibrations, the energies of these CF levels could be determined. The CF state 1Γ 8 of the ground multiplet 4 I 9/2 of [LaCp 3 (NCCH 3 ) 2 :Nd 3+ ], which previously could not be detected by absorption measurements, could be derived from the luminescence transition 4 F 3/2 → 4 I 9/2 . Considering these additional assignments, the goodness of the fit increased from 32.3 to 29.9 cm −1 for 61 assignments.

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Section: Skelettschwingungenunclassified

Zur Elektronenstruktur metallorganischer Komplexe der ƒ -Elemente, 81. Berechnung der Normalschwingungen von La(η⁵-C₅H₅)₃(NCCH₃)₂ auf der Basis der Dichtefunktionaltheorie sowie vibronische Kopplungen und Auffindung weiterer rein elektronischer Absorptions- und Lumineszenzüberg¨ange bei [La(η⁵-C₅H₅)₃(NCCH₃)₂:Nd³⁺] / Electronic Structures of Organometallic Complexe

Amberger

Reddmann

2013

Zeitschrift Für Naturforschung B

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“…9,13 The ferrocene molecule as a whole virtually stays at the same position, and there are no significant changes in the zeolite fragment. The structure found from the refinements indeed corresponds to an energy minimum.…”

Section: Figmentioning

confidence: 99%

“…These values are typical for CH-O interactions. 15 Former DFT calculations on a single ferrocene molecule show that the energy difference for rotation of the rings from 9°to 0°is almost zero, 9 and rather weak hydrogen bonds could well explain the eclipsed ring orientation of ferrocene in zeolite Y. The Coulombic interaction between the The large dots show the four sodium ions in the supercage forming a tetrahedron, and are also shown in Fig.…”

Section: Figmentioning

confidence: 99%

“…The difference in total energy between the bare fragment added with the total energy of a single ferrocene molecule as calculated before 9 and the fragment with a ferrocene molecule amounts to Ϫ130 kJ mol Ϫ1 . This compares well with the measured sorption energy of benzene molecules in NaY zeolite, which is around Ϫ77 kJ mol Ϫ1 .…”

Section: Figmentioning

confidence: 99%

“…In the final refinement the geometry of the ferrocene molecule was constrained according to the known geometry of a single ͑eclipsed͒ ferrocene molecule 9 and x-ray data, respectively. We do not include the hydrogen atoms of the cyclopentadienyl rings in the refinement on the x-ray pattern due to their very low scattering factor.…”

Section: Structure Determinationmentioning

confidence: 99%

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Localization of ferrocene in NaY zeolite by powder x-ray and neutron diffraction

Kemner

Overweg

Eijck

et al. 2002

The Journal of Chemical Physics

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We study the inclusion of the metallocene ferrocene Fe͑C 5 H 5 ) 2 molecules in the supercages of NaY zeolite. To find the exact location of the ferrocene molecules within the supercages we perform neutron and powder x-ray diffraction on bare NaY zeolite, and on NaY zeolite loaded with one or two ferrocene molecules per supercage. Using the complementary properties of both techniques we show that the ferrocene molecules are located just above a line joining two neighboring sodium ions at the SII positions in the zeolite supercage. The C 5 H 5 rings are oriented towards the sodium ions in an ordered manner. This structure is confirmed by quantum chemistry calculations. The geometry of the ferrocene molecules barely changes, indicating that the increased reactivity of ferrocene upon adsorption in a zeolite is thus a result of the position of the molecules. The main interactions responsible for this position are Coulombic attraction and hydrogen bonding. The inclusion of ferrocene in a Y-type zeolite provides a homogeneous distribution of iron throughout the zeolite at well-defined locations.

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Atom-Selective Vibrational Spectroscopy: Ferrocene Probed via the Iron Atom

et al. 2001

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The vibrational spectrum of solid ferrocene by inelastic neutron scattering

Cited by 39 publications

References 13 publications

Localization of ferrocene in NaY zeolite by powder x-ray and neutron diffraction

Atom-Selective Vibrational Spectroscopy: Ferrocene Probed via the Iron Atom

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