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Deghoul, F.; Chermette, Henry; Rogemond, F.; Moncorgé, R.; Stückl, Claudia; Daul, Claude

doi:10.1103/physrevb.60.2404

Cited by 17 publications

(3 citation statements)

References 30 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%

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%

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

Deeth

2003

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“…DFT gives a good description of the ground electronic state and, even though the density functional theorem formally refers only to this ground state, DFT is being applied to excited states with considerable success. [4][5][6][7][8][9][10][11][12] Recent innovations both in functional design and in the range of properties which can be computed from first principles, particularly electron paramagnetic resonance (EPR) 13 and nuclear magnetic resonance parameters, 14 polarisabilities and excited states, 15 provide a powerful computational tool for TM species.…”

Section: Introductionmentioning

confidence: 99%

A combined ligand field and density functional theory study of the structural and spectroscopic properties of [Cu(dien)2]2+

Deeth

2001

J. Chem. Soc., Dalton Trans.

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“…For the past decade, great attention has been paid to materials activated with 3d 2 transition metal ions (e.g., Cr 4+ , Mn 5+ , and Fe 6+ ) because of their applicability as tunable solid-state lasers in the near-infrared (NIR) range. There have appeared numerous studies of the spectroscopy [1][2][3][4][5][6][7][8][9][10][11], electron spin resonance [12][13][14], and high-pressure luminescence spectroscopy [15][16][17][18][19] of the 3d 2 -activated materials.…”

Section: Introductionmentioning

confidence: 99%

The effect of pressure on vibrational modes in Li₃PO₄

Smith¹,

Shen²,

Bray³

2001

J. Phys.: Condens. Matter

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We have studied the effect of pressure on the stretching and bending modes of (PO4)3- molecular groups in undoped Li3PO4 and (MnO4)3- groups in Mn5+-doped Li3PO4 using Raman spectroscopy and luminescence. The high-pressure Raman spectroscopy study confirmed an irreversible phase transition from the high-temperature phase to the low-temperature phase, observed in our previous high-pressure luminescence study (Riedener T, Shen Y R, Smith R J and Bray K L 2000 Chem. Phys. Lett. 321 445) and further characterized the rate and irreversibility of the phase transition. We observed and analysed vibronic transitions occurring in the 1E emission of Mn5+ in both phases. A stronger vibronic transition associated with the bending mode is interpreted in terms of an E⊗e Jahn-Teller coupling. Bulk and local compressibilities were predicted from variations of the energies of the (PO4)3- and (MnO4)3- stretching modes with pressure.

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Metal-centered and ligand-to-metal charge-transfer transitions of[CrO4]4−and

Cited by 17 publications

References 30 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

A combined ligand field and density functional theory study of the structural and spectroscopic properties of [Cu(dien)2]2+

The effect of pressure on vibrational modes in Li₃PO₄

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Metal-centered and ligand-to-metal charge-transfer transitions of[CrO4]4−and

Cited by 17 publications

References 30 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

A combined ligand field and density functional theory study of the structural and spectroscopic properties of [Cu(dien)2]2+

The effect of pressure on vibrational modes in Li3PO4

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The effect of pressure on vibrational modes in Li₃PO₄