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

Abstract

The classic metallocene, ferrocene (see picture), has been studied by Nuclear Inelastic Absorption Spectroscopy (NIS), a vibrational spectroscopic technique. This technique is sensitive only to iron motion and allows for the characterization of important, low frequency iron modes.

Dynamics of metal centers monitored by nuclear inelastic scattering

“…1) are in reasonable agreement with the experimental spectra given in ref. [12]. The comparison of calculated IR, Raman and NIS spectra in the region of metal-ligand vibrations exemplifies the complementarity of NIS and Raman spectra.…”

“…The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21][22][23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

“…With the example of the ferrocene molecule we demonstrate here that these mechanical properties are more easily calculated with sufficient accuracy than those electric properties (changes of dipole moment or polarizability tensor) that are needed for the simulation of IR or Raman spectra. The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21-23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

Dynamics of metal centers monitored by nuclear inelastic scattering

“…1) are in reasonable agreement with the experimental spectra given in ref. [12]. The comparison of calculated IR, Raman and NIS spectra in the region of metal-ligand vibrations exemplifies the complementarity of NIS and Raman spectra.…”

“…The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21][22][23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

“…With the example of the ferrocene molecule we demonstrate here that these mechanical properties are more easily calculated with sufficient accuracy than those electric properties (changes of dipole moment or polarizability tensor) that are needed for the simulation of IR or Raman spectra. The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21-23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

Dynamics of metal centers monitored by nuclear inelastic scattering

“…1) are in reasonable agreement with the experimental spectra given in ref. [12]. The comparison of calculated IR, Raman and NIS spectra in the region of metal-ligand vibrations exemplifies the complementarity of NIS and Raman spectra.…”

“…The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21][22][23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

“…With the example of the ferrocene molecule we demonstrate here that these mechanical properties are more easily calculated with sufficient accuracy than those electric properties (changes of dipole moment or polarizability tensor) that are needed for the simulation of IR or Raman spectra. The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21-23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

Dynamics of metal centers monitored by nuclear inelastic scattering

“…1) are in reasonable agreement with the experimental spectra given in ref. [12]. The comparison of calculated IR, Raman and NIS spectra in the region of metal-ligand vibrations exemplifies the complementarity of NIS and Raman spectra.…”

“…The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21][22][23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”

“…With the example of the ferrocene molecule we demonstrate here that these mechanical properties are more easily calculated with sufficient accuracy than those electric properties (changes of dipole moment or polarizability tensor) that are needed for the simulation of IR or Raman spectra. The dynamics of the iron center in ferrocene has been studied intensively by various spectroscopic techniques including NIS [12] and quasielastic nuclear forward scattering [13]. We have performed DFT calculations using the hybrid functional B3LYP [14] together with five different basis sets, 3-21G [15][16][17][18][19][20], CEP-31G [21-23], 6-311G [24,25] (with the Wachters-Hay double zeta basis for Fe [26,27]), TZV and TZVP [28,29] as included in the Gaussian 03 program package [30].…”