Vibronic Interactions in Vanadium Tetrachloride by Gas Electron Diffraction

Morino, Yonezo; Uehara, Hiromichi

doi:10.1063/1.1727535

Cited by 120 publications

(39 citation statements)

References 18 publications

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“…In summary this shows that DFT calculations for this simple molecule, with a relatively small JT effect, yields results in good agreement with the experiments [4,16,48,61]. E JT D 50:8 cm 1 is obtained by the DFT calculation and the …”

Section: Tetrachlorovanadium(iv) Vclsupporting

confidence: 75%

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Zlatar

Schläpfer

Daul

2009

Springer Series in Chemical Physics

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A new method for the analysis of the adiabatic potential energy surfaces of Jahn-Teller (JT) active molecules is presented. It is based on the analogy between the JT distortion and reaction coordinates. Within the harmonic approximation the JT distortion can be analysed as the linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Contribution of the normal modes to the distortion, their energy contribution to the JT stabilisation energy, the forces at high symmetry cusp and detailed distortion path can be estimated quantitatively. This approach gives direct insight into the coupling of electronic structure and nuclear displacements. Further more, it is reviewed how multideterminental DFT can be applied for the calculation of the JT parameters. As examples the results for VCl 4 , cyclopentadienyl radical and cobaltocene are given.

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Section: Tetrachlorovanadium(iv) Vclsupporting

confidence: 75%

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Zlatar

Schläpfer

Daul

2009

Springer Series in Chemical Physics

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“…"Differences of up to 0.05 A are found between Ti-CI bond lengths in gas phase and solid state TiCl, (23). Thus part of the increase in R(Ti-CI) in the species containing Cp rings may be associated with extramolecular relaxation in the solid state.…”

Section: Introductionmentioning

confidence: 84%

“…Our goal was to use the measured spectral shape to further distinguish between these two models and, ideally, to learn which has greater predictive power. "Gas phase electron diffraction (23). "Solid state X-ray diffraction (24).…”

Section: Introductionmentioning

confidence: 99%

“…The default Huckel parameters were used, except that C1 3d orbitals were included in the basis set since previously this was found to be important in obtaining correct (relative) energies for the lower energy unoccupied orbitals (22). The geometries were taken from gas phase electron diffraction or solid state X-ray diffraction data reported in the literature (23)(24)(25) and are summarized in Table 1. To facilitate interpretation of the core spectra, EHMO calculations relevant to the core excited states were carried out within the equivalent ionic core virtual orbital (EICVOM) model (26).…”

Section: Introductionmentioning

confidence: 99%

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Inner shell spectroscopy of (η⁵-C₅H₅)₂TiCl₂, (η⁵-C₅H₅)TiCl₃, and TiCl₄

Wen¹,

Hitchcock²

1993

Can. J. Chem.

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,, CpTiCl,, and TiC1, have been derived from electron energy loss spectra recorded under electric dipole scattering conditions. The C Is spectra are interpreted with the aid of semiempirical extended Hiickel calculations and comparisons with the C 1s spectra of other cyclopentadienyl complexes. The Ti 2p spectra are interpreted using the extended Hiickel results and comparisons with atomic multiplet -crystal field calculations for ~i , ' taken from the literature.A.T. WEN et A.P. HITCHCOCK. Can. J. Chem. 71, 1632Chem. 71, (1993.Utilisant les spectres relatifs 2 la perte d'knergie klectronique enregistrks dans des conditions de diffusion des dipBles Clectriques, on a determink les forces de l'oscillateur pour l'excitation C 1s du Cp2TiC1, et du CpTiCl, en phase gazeuse (Cp = T&H,) et les excitations C1 2p et Ti 2p du Cp2TiC1,, du CpTiCl, et du TiCl, en phase gazeuse. On interprete les spectres C 1s a l'aide des calculs semi-empiriques Ctendus de Hiickel et des comparaisons des spectres C 1s d'autres complexes du cyclopentadiknyle. On interprkte les spectres Ti 2p en utilisant des rksultats de Hiickel Ctendus et des comparaisons avec des calculs multiplet atomique -champ cristallin pour le ~i " ' tires de la litterature.[Traduit par la rkdaction]

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“…The important geometrical parameters of these complexes, optimized or simulated by using the BP86 functional, are collected in Tables 2-5, together with corresponding www.chemeurj.org data observed in the gas phase [37,[52][53][54][55][56][57][58][59][60][61][62] or in the solid state. [63][64][65][66][67][68][69] The tables include the equilibrium bond lengths computed with both Gaussian98 and the CPMD program, as well as zero-point corrected and thermal averaged bond lengths.…”

Section: Geometriesmentioning

confidence: 99%

Thermal Effects and Vibrational Corrections to Transition Metal NMR Chemical Shifts

Grigoleit

Bühl

2004

Chemistry A European J

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Both zero-point and classical thermal effects on the chemical shift of transition metals have been calculated at appropriate levels of density functional theory for a number of complexes of titanium, vanadium, manganese and iron. The zero-point effects were computed by applying a perturbational approach, whereas classical thermal effects were probed by Car-Parrinello molecular dynamics simulations. The systematic investigation shows that both procedures lead to a deshielding of the magnetic shielding constants evaluated at the GIAO-B3 LYP level, which in general also leads to a downfield shift in the relative chemical shifts, delta. The effect is small for the titanium and vanadium complexes, where it is typically on the order of a few dozen ppm, and is larger for the manganese and iron complexes, where it can amount to several hundred ppm. Zero-point corrections are usually smaller than the classical thermal effect. The pronounced downfield shift is due to the sensitivity of the shielding of the metal centre with regard to the metal-ligand bond length, which increase upon vibrational averaging. Both applied methods improve the accuracy of the chemical shifts in some cases, but not in general.

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Vibronic Interactions in Vanadium Tetrachloride by Gas Electron Diffraction

Cited by 120 publications

References 18 publications

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Inner shell spectroscopy of (η⁵-C₅H₅)₂TiCl₂, (η⁵-C₅H₅)TiCl₃, and TiCl₄

Thermal Effects and Vibrational Corrections to Transition Metal NMR Chemical Shifts

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Vibronic Interactions in Vanadium Tetrachloride by Gas Electron Diffraction

Cited by 120 publications

References 18 publications

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Inner shell spectroscopy of (η5-C5H5)2TiCl2, (η5-C5H5)TiCl3, and TiCl4

Thermal Effects and Vibrational Corrections to Transition Metal NMR Chemical Shifts

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Inner shell spectroscopy of (η⁵-C₅H₅)₂TiCl₂, (η⁵-C₅H₅)TiCl₃, and TiCl₄