Ground State and Excited Stated Properties of Hexaamminechromium(III) Ion:  A Density Functional Study

Doclo, Karel; Corte, David De; Daul, Claude; Güdel, Hans-Ueli

doi:10.1021/ic9715207

Cited by 17 publications

(8 citation statements)

References 47 publications

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“…Neither approach gave particularly good absolute results both underestimating transition energies by between 3000 to 7000 cm À1 . However, the errors are comparable to those reported for other TM complexes 44,64,[70][71][72][73][74] and it may be too much to expect present methodology to be more accurate. Presumably, the fault lies with the currently available functionals.…”

Section: Discussionsupporting

confidence: 78%

“…Ziegler et al 62 described an approximate method for obtaining multiplet energies by computing the energies of suitable determinants. The method has been extended by Daul 43 and is reasonably accurate 63,64 but limited in that if there are two or more states with identical spatial and spin properties, it cannot resolve the possible configurational mixing which may exist. However, this issue has been resolved, at least in principle, with the advent of time dependent DFT (TDDFT).…”

Section: Excited D Statesmentioning

confidence: 99%

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Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Deeth

2003

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The d-orbital energy sequences for low symmetry transition metal complexes derived from Kohn-Sham density functional theory and ligand field theory are different due to each model's treatment of interelectron repulsion. The implications for providing a unified description of the underlying metal-ligand bonding are analysed and illustrated using conventional and time-dependent DFT. Previous detailed spectroscopic studies have established the d orbital sequence in planar coordination complexes containing pi-donor halide ligands as dx2-y2 >> dxy > dxz, dyz > dz2 while for a sigma-only system like [Pd(NH3)4]2+, ligand field approaches like the angular overlap model (AOM) or cellular ligand field (CLF) model predict dxz, dyz, and dxy, should be degenerate. However, the energies of the Kohn Sham (KS) 'd' orbitals of [PdCl4]2- and [Pd(NH3)4]2+ place dxy below the dxz/dyz pair. Direct use of the KS orbital eigenvalues in AOM or CLF analyses would imply both ligands are pi acceptors. This result is independent of the choice of functional or whether the calculation is carried out in vacuo or in a polarised continuum representing solvation by water. The origin of the difference between the KS and LFT d orbital sequences derives from their treatments of d-d interelectron repulsion. KS orbitals include interelectron repulsion contributions while LFT d orbitals do not. For a low-spin d8 complex, DFT gives less d-d interelectron repulsion in the xy plane leading to a lowering of dxy relative to dxy/dyz. This differential effect can be reversed qualitatively by progressively removing electron density from dz2 and placing it in dx2-y2. When about 0.6 electrons is rearranged, E(dxy) > E(dxz/dyz) for [PdCl4]2- and the dpi orbitals for [Pd(NH3)4]2+ are virtually degenerate. The wider ramifications of these interelectron repulsion effects are discussed for other symmetries. Excited d state energies for [PdCl4]2- are computed using both time dependent density functional theory (TDDFT) and determinant energies. The latter give the experimental sequence 1A2g < 1Eg < 1B1g while TDDFT gives 1Eg < 1A2g < 1B1g. Both give transition energies up to 30% lower than observed. A DFT analysis of the bonding energies in [PdCl4]2- indicates that the Pd-Cl pi bonding in the molecular plane is about 33% weaker than the out-of-plane pi interaction due to non-zero overlap between ligand orbitals. The normal LFT assumption of linear ligation may not always be valid.

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Section: Discussionsupporting

confidence: 78%

Section: Excited D Statesmentioning

confidence: 99%

Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Deeth

2003

Faraday Disc.

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“…All calculations described in this work were performed on Linuxbased Pentium III 600 MHz computers with the Amsterdam Density Functional (ADF) program, version ADF2000, 32 developed by Baerends et al 33 All calculations employed the local density approximation (LDA) to the exchange potential, 34 and the correlation potential of Vosko, Wilk, and Nusair. 35 Previous studies 13,[36][37][38][39][40][41][42][43] and our own ongoing investigations 44 have shown that, for several classes of inorgranic compounds but particularly for structural features of anionic metal-containing complexes, 13,42,43 Basis sets for all atoms were of triple-ζ quality with Slater-type orbitals. Electrons in orbitals up to and including 2p {Cl, V}, 3d {Nb}, and 4d {Ta} were treated in accordance with the frozencore approximation.…”

Section: Computational Detailsmentioning

confidence: 96%

Factors Affecting Metal−Metal Bonding in the Face-Shared d³d³ Bioctahedral Dimer Systems, MM‘Cl₉⁵^- (M, M‘ = V, Nb, Ta)

Petrie

Stranger

2002

Inorg. Chem.

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Density functional theory (DFT) calculations have been used to investigate the d(3)d(3) bioctahedral complexes, MM'Cl(9)(5-), of the vanadium triad. Broken-symmetry calculations upon these species indicate that the V-containing complexes have optimized metal-metal separations of 3.4-3.5 A, corresponding to essentially localized magnetic electrons. The metal-metal separations in these weakly coupled dimers are elongated as a consequence of Coulombic repulsion, which profoundly influences (and destabilizes) the gas-phase structures for such dimers; nevertheless, the intermetallic interactions in the V-containing dimers involve significantly greater metal-metal bonding character than in the analogous Cr-containing dimers. These observations all show good agreement with existing experimental (solid state) results for the chloride-bridged, face-shared dimers V(2)Cl(9)(5-) and V(2)Cl(3)(thf)(6)(+). In contrast to the V-containing dimers, complexes featuring only Nb and Ta have much shorter intermetallic distances (approximately 2.4 A) consistent with d-electron delocalization and formal metal-metal triple bond formation; again, good agreement is found with available experimental data. Calculations on the complexes V(2)(mu-Cl)(3)(dme)(6)(+), Nb(2)(mu-dms)(3)Cl(6)(2-), and Ta(2)(mu-dms)(3)Cl(6)(2-), which are closely related to compounds for which crystallographic structural data exist, have been pursued and provide an insight into the intermetallic interactions in the experimentally characterized complexes. Analysis of the contributions from d-orbital overlap (E(ovlp)) stabilization, as well as spin polarization (exchange) stabilization of localized d electrons (E(spe)), has also been attempted for the MM'Cl(9)(5-) dimers. While E(ovlp) clearly dominates over E(spe) as a stabilizing factor in those dimers containing only Nb and Ta metal atoms, detailed assessment of the competition between E(ovlp) and E(spe) for V-containing dimers is obstructed by the instability of triply bonded V-containing dimers against Coulombic explosion. On the basis of the periodic trends in E(ovlp) versus E(spe), the V-triad dimers have a greater propensity for metal-metal bonding than do their Cr-triad or Mn-triad counterparts.

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“…Another significant calculation was of the spin-orbit interaction between the 4 E g state and the upper 2 B 1g component of the 2 E g state, which conferred 3.4% t 2g 2 e g 1 character upon the latter. Recently another density functional calculation on this molecule has appeared, 154 and in this work the geometry was allowed to optimize. The bond lengths, the sequence of d-d excitation energies, and the tetragonal distortion of the 4 T 2g excited state were well reproduced, but the calculated transition energies and vibrational frequencies differed significantly from the experimental values.…”

Section: Theoretical Studiesmentioning

confidence: 99%

Photochemistry and Photophysics of Chromium(III) Complexes

1999

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Ground State and Excited Stated Properties of Hexaamminechromium(III) Ion: A Density Functional Study

Cited by 17 publications

References 47 publications

Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Factors Affecting Metal−Metal Bonding in the Face-Shared d³d³ Bioctahedral Dimer Systems, MM‘Cl₉⁵^- (M, M‘ = V, Nb, Ta)

Photochemistry and Photophysics of Chromium(III) Complexes

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Ground State and Excited Stated Properties of Hexaamminechromium(III) Ion: A Density Functional Study

Cited by 17 publications

References 47 publications

Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Ligand field and density functional descriptions of the d-states and bonding in transition metal complexes

Factors Affecting Metal−Metal Bonding in the Face-Shared d3d3 Bioctahedral Dimer Systems, MM‘Cl95- (M, M‘ = V, Nb, Ta)

Photochemistry and Photophysics of Chromium(III) Complexes

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Factors Affecting Metal−Metal Bonding in the Face-Shared d³d³ Bioctahedral Dimer Systems, MM‘Cl₉⁵^- (M, M‘ = V, Nb, Ta)