g-tensor theory for strongly distorted octahedral low-spind 5 complexes

Bernhardt, Eduard; Komozin, P. N.

doi:10.1007/bf02578498

Cited by 1 publication

(4 citation statements)

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“…However, when D 3 d distortion with a singly occupied 3d z 2 orbital is assumed, the parameters derived from theoretical considerations (Table ) agree nicely with our ab initio data in Tables , , and 6. Furthermore, according to the ligand-field model, the observed g ⊥ and g ∥ values imply an orbital reduction factor k = 0.64 and a ratio Δ/ξ = 11.3 (Table ). The latter value, together with ξ ≈ 100 cm -1 , affords an estimate for Δ of ca.…”

Section: Discussionmentioning

confidence: 97%

“…However, for V(CO) 6 isolated in a CO matrix at 4 K, further evidence for D 3 d symmetry can be obtained from a deeper analysis of the experimental ESR spectrum . Our analysis is based on a minimum-basis-set ligand-field model of g tensors and hyperfine couplings in octahedral low-spin d 5 complexes . Within the framework of this model, both experimental ESR parameters, the g tensors g ⊥ = g x = g y and g ∥ = g z , and the hyperfine coupling constants A ⊥ = A x = A y and A ∥ = A z can be used to estimate (i) the energies Δ (splitting of the d π level in an axial ligand field) and Δ te (difference between d π and d σ levels in an approximately octahedral d 5 complex), (ii) the spin−orbit coupling constants ξ and ξ te inside d π and between the d π and d σ levels, (iii) the k-orbital reduction factor, and (iv) the Fermi contact term K k and the parameter for dipole−dipole interaction P = P d (for d electrons).…”

Section: Discussionmentioning

confidence: 98%

“… a | g | and | A | from ref ; note that the signs correspond to the convention adopted in ref , which differs from that of refs and used to generate the data in Table . b For a definition of the parameter ω, see ref ; results for two limiting, estimated values are shown. c There is an alternative sign for A ∥ possible, resulting in alternative values given in brackets.…”

Section: Discussionmentioning

confidence: 99%

“…For example, the negative sign of the g values of NpF 6 was determined experimentally ( g = −0.604(3)) by using circularly polarized radiation . The convention of signs for g values of d 5 complexes with O h symmetry is g x = g y = g z = g . Another convention is used in refs and (e.g., g x , g y , and g z are positive for complexes with low orbital contributionsnearly pure spin g tensors).…”

Section: Discussionmentioning

confidence: 99%

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D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

et al. 2003

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Structures, relative energies, vibrational spectra, and ESR parameters of the 17emolecule V(CO) 6 in O h , D 3d , D 4h , and D 2h symmetry have been computed with density functional and high-level ab initio methods. At all theoretical levels applied, the same energetic order is obtained, D 3d < D 2h < D 4h < O h , with the D 2h structure as a transition state connecting equivalent D 3d species. At the RCCSD(T)/AE2 level using UBP86/ AE2 geometries, the energies of the D 2h , D 4h and O h species relative to that of D 3d minimum are predicted to be 210, 535, and 731 cm -1 , respectively. According to molecular dynamics simulations on the UBP86/AE1 potential energy surface, the D 3d minimum is preserved at very low temperatures (around 16 K), whereas at 300 K the molecule is highly fluxional with an averaged structure indistinguishable from that of [V(CO) 6 ]with its O h symmetric ground state. Nearly complete IR and Raman spectra of V(CO) 6 and V( 13 CO) 6 have been recorded at 300 K for the first time in the gas phase, in solution, and at cryogenic temperatures in Ne and Ar matrices. The spectra show a pronounced temperature dependence, especially for the Jahn-Teller active modes, E g and T 2g . The observed infrared matrix spectra generally agree well with the calculated spectrum (BP86/AE2 level) for the D 3d structure and much less with that of the D 4h isomer. The A 1g modes in the Raman spectra are reasonably well reproduced computationally in the harmonic approximation, whereas this approximation breaks down for the E g and T 2g bands, as expected. Further evidence for the D 3d symmetry of V(CO) 6 is obtained from a reanalysis of the experimental ESR spectrum that is reported in the literature. The observed ordering of the hyperfine coupling constants A | and A ⊥ is reproduced theoretically only when distortion to D 3d symmetry is assumed. In addition, the bonding properties of V(CO) 6 are compared to those of [V(CO) 6 ]and Cr(CO) 6 .

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Section: Discussionmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 98%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 2 more Smart Citations

D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

et al. 2003

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g-tensor theory for strongly distorted octahedral low-spind 5 complexes

Cited by 1 publication

References 14 publications

D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

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g-tensor theory for strongly distorted octahedral low-spind 5 complexes

Cited by 1 publication

References 14 publications

D3d Ground-State Structure of V(CO)6: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

D3d Ground-State Structure of V(CO)6: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

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D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect

D₃_d Ground-State Structure of V(CO)₆: A Combined Matrix Isolation and ab Initio Study of the Jahn−Teller Effect