Optical Spectra of Ni(CO)<sub>4</sub> and Cr(CO)<sub>6</sub> Revisited

Pierloot, Kristine; Tsokos, E; Vanquickenborne, L. G.

doi:10.1021/jp9614355

Cited by 96 publications

(152 citation statements)

References 30 publications

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“…Other TDDFT calculations with the ADF program on transition metal compounds are in progress. Of these, we just mention the TDDFT results for Cr(CO) 6 , 25,75,76 which reconfirm the assignments based on the CASPT2 69 and DFT-∆SCF 77 approaches, thus challenging the long-standing assignments by Beach and Gray 43,44 on the nature of the lowest excited states of these systems. The TDDFT results are, in this case, in much better agreement with the experimental and CASPT2 values than the ∆SCF results are.…”

Section: Resultsmentioning

confidence: 76%

“…In contrast to this, INDO/S CI 86 yields six of such states, CASSCF 69 yields zero (! ), and SECI yields two.…”

Section: Excitation Energies Of This Molecule Which Has T D Symmetrymentioning

confidence: 97%

“…The SECI results are too high in energy and much poorer than the SAC-CI results of Table 4. In ref 69, CASSCF results are also reported (based upon CASSCF calculations for the excited states), but they are in quite poor agreement with the experimental values, being typically 2-3 eV too high. The authors of ref 69 attribute this to an active space that is too limited, which, with current computer resources, cannot be helped.…”

Section: Excitation Energies Of This Molecule Which Has T D Symmetrymentioning

confidence: 97%

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Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

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The first time-dependent density functional theory (TDDFT) calculations on the spectra of molecules containing transition metals are reported. Three prototype systems are considered, of which the assignments are controversial: MnO 4 -, Ni(CO) 4 , and Mn 2 (CO) 10 . The TDDFT results are shown to be comparable in accuracy to the most elaborate ab initio calculations and lead to new insights in the spectra of these molecules. In some cases, the presented TDDFT results differ substantially, in both the ordering and the values for the excitation energies, from the older DFT method for the calculation of excitation energies: the ∆SCF approach. For the Mn 2 (CO) 10 molecule, the presented results are the highest-level theoretical results published so far. Over all, the results show that TDDFT can be a very useful tool in the calculation and interpretation of the spectra of transition metal compounds.

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Section: Resultsmentioning

confidence: 76%

“…In contrast to this, INDO/S CI 86 yields six of such states, CASSCF 69 yields zero (! ), and SECI yields two.…”

Section: Excitation Energies Of This Molecule Which Has T D Symmetrymentioning

confidence: 97%

Section: Excitation Energies Of This Molecule Which Has T D Symmetrymentioning

confidence: 97%

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Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

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“…A very clear example is Cr(CO) 6 , where we have recently found 48 precisely the same situation to apply: the ligand-field excited states are at R e at high energy, but they descend so rapidly upon Cr-CO bond lengthening that they very soon cross the lowest excited state, which has CT character at R e , so that the lowest excited state PEC becomes dissociative. Recent sophisticated CASSCF/ CASPT2 calculations of the optical spectrum of Cr(CO) 6 by Pierloot et al 49 provide support for this reassessment of the role of LF states in the photochemical metal-carbonyl dissociation process in that they show that the LF excited states of Cr(CO) 6 arescontrary to the original assignment by Beach and Gray 50 slocated rather high in the spectrum, the photodissociative lowest excited states having clear CT character at R e . IC960688+…”

Section: Discussionmentioning

confidence: 79%

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)

et al. 1997

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Density functional calculations have been performed on the ground and excited states of MnCl(CO) 5 in order to explain the photochemistry of MX(CO) 5 complexes (M ) Mn, Re; X ) Cl, Br, I). As found earlier for Mn 2 -(CO) 10 (Inorg. Chem. 1996, 35, 2886, the e g -type unoccupied 3d orbitals in the pseudooctahedral environment are located rather high in the virtual orbital spectrum, and the corresponding ligand-field (LF) excitations are more than 1 eV above the lowest excitations. Potential energy curves (PECs) nevertheless show that the lowest excited states, which involve transitions to the Mn-Cl σ* orbital at equilibrium geometry, are dissociative for axial and equatorial CO loss. The mechanism is again, as in Mn 2 (CO) 10 , a strongly avoided crossing of the lowest excited state (a 1,3 E) with the higher dissociative LF states (different ones for CO ax and CO eq dissociation) which rapidly descend upon Mn-CO bond lengthening. In spite of the lowest excitation being to the Mn-Cl σ*-orbital, Mn-Cl homolysis cannot occur out of the lowest excited state. The photochemical behavior of Mn 2 -(CO) 10 , MnH(CO) 5 , and MnCl(CO) 5 is compared. The mechanisms of CO loss are found to be very similar, but there is a large difference with respect to the breaking of the σ bond (Mn-Mn, Mn-H, or Mn-Cl). Only in the case of Mn 2 (CO) 10 , the lowest broad absorption band contains the σ f σ* excitation and leads to σ bond breaking.

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“…26 Analysis of the bond length change in the ligand field excited state of [PtCl 3 (CO)] -showed that the metal-carbon distance increased by 0.18 Å. 10 All of the above bond length changes, with the exception of those in Mo(CO) 6 and W(CO) 6 , 24,25 occur in excited states assigned as primarily d-d in character. The picture that is emerging is that the changes in the metalcarbon bond lengths in ligand field excited states of metalcarbonyl complexes are between about 5% and 10% of the bond length.…”

mentioning

confidence: 99%

Luminescence of the Nonclassical Homoleptic Metal Carbonyl Complex [Rh(CO)₄]⁺

Bitner

Zink²,

Havighurst³

et al. 2002

Inorg. Chem.

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The nonclassical [Rh(CO)(4)](+) cation is luminescent at low temperature with a peak maximum at 19640 cm(-1) and a full-width at half-maximum of 2900 cm(-1). Both the solution absorption and low-temperature solid-state luminescence spectra of the [Rh(CO)(4)](1-Et-CB(11)F(11)) salt are reported. The cesium salt of the [1-Et-CB(11)F(11)](-) counterion is also luminescent (with a peak maximum at 22650 cm(-1)), but the emission maximum of [Rh(CO)(4)](+) is lower in energy. The Rh-C bond length changes of approximately 0.07 A in the excited state are calculated. The calculated bond length changes in the nonclassical [Rh(CO)(4)](+) ion are not very different from those in classical complexes.

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Optical Spectra of Ni(CO)₄ and Cr(CO)₆ Revisited

Cited by 96 publications

References 30 publications

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)

Luminescence of the Nonclassical Homoleptic Metal Carbonyl Complex [Rh(CO)₄]⁺

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Optical Spectra of Ni(CO)4 and Cr(CO)6 Revisited

Cited by 96 publications

References 30 publications

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)5)

Luminescence of the Nonclassical Homoleptic Metal Carbonyl Complex [Rh(CO)4]+

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Optical Spectra of Ni(CO)₄ and Cr(CO)₆ Revisited

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)

Luminescence of the Nonclassical Homoleptic Metal Carbonyl Complex [Rh(CO)₄]⁺