On the Molecular Structure of Dimanganese Decarcarbonyl, Mn2(CO)10.

Almenningen, A.; Jacobsen, G. G.; Seip, H. M.; Lindblad, Carl-Gunnar; Lindberg, Alf A.; Jansen, Gert; Lamm, Bo; Samuelsson, Benny

doi:10.3891/acta.chem.scand.23-0685

Cited by 51 publications

(54 citation statements)

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“…27 The other experimental determinations of the Mn-Mn bond length by X-ray diffraction at room temperature 28 and at 74 K 29 give shorter bonds, i.e., 2.923 and 2.895 Å, respectively. Previous theoretical studies stressed that the Mn-Mn bond has a very shallow potential well.…”

Section: Resultsmentioning

confidence: 99%

“…Table 6 collects the results of our calculations along with the structural data obtained by X-ray diffraction at 74 K 29 and by electron diffraction in the gas phase. 27 The experimental parameters shown in the table are averaged over bond lengths and bond angles that would be equivalent in perfect D 4d symmetry. The uncertainties are given in brackets.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

et al. 1996

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The basis set superposition error (BSSE) for the Cr(CO) 5 -CO and (CO) 5 Mn-Mn(CO) 5 bonds is calculated for a large variety of STO basis sets. All investigated metal basis sets, being at least TZ for 3d and DZ for 4s are adequate. Ligand basis sets of TZD quality or better are required in order to have a low BSSE (6-8 kJ/mol or less) for both the metal-ligand and the metal-metal bond. When the ligand s, p basis set is of double-quality, the BSSE is significant for the metal-ligand bond (16-22 kJ/mol depending on the polarization functions), but it is partly canceled by a basis set incompleteness error of opposite sign. For the metal-metal bond, the BSSE for DZ s, p ligand bases is unacceptably large (33-57 kJ/mol), leading to much too high bond energies if no correction for BSSE is applied. In general, the bond energies after correction for BSSE are rather stable. It is remarkable that for the metal-metal bond, but not for the metal-ligand bond, there is for all pure s, p ligand bases after correction for the BSSE a discernible basis set incompleteness error (ca. 15 kJ/mol), which only disappears after adding at least one polarization function. Agreement of the converged results for both geometries and bond energies with experiment is excellent.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

et al. 1996

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“…The molecule of Mn 2 (CO) 10 exists in a struc-ture with D 4d symmetry (Scheme 1), and the same structure was also found for the optimized geometry in our calculations. The calculated geometrical parameters, together with the corresponding experimental values, 22,40,41 are summarized in the Table 1. The agreement between experimental and calculated values is fairly satisfactory.…”

Section: Computationsmentioning

confidence: 99%

Chemical structures from the analysis of domain‐averaged fermi holes. Nature of the MnMn bond in bis(pentacarbonylmanganese)

2005

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Abstract:Because of conflicting and contradictory classification based on traditional AIM characteristics, the nature of the Mn-Mn bond has been and still is the subject of continuing discussions. To overcome the existing inconsistencies in the interpretation of the nature of this bond, the bonding in Mn 2 (CO) 10 has been analyzed and discussed in terms of new recently proposed methodology known as the analysis of domain-averaged Fermi holes. It has been shown that this analysis is able to reconcile the conflicting conclusions of earlier AIM-based studies with traditional anticipations based on simple electron counting rules. According to Fermi hole analysis, the Mn-Mn bond has the character of the more or less ordinary covalent single bond, but the analysis also brings clear evidence in favor of Mn ⅐ ⅐ ⅐ (CO) intramolecular interactions between the metal atom and the ligands bonded to the other metal atom. These interactions could be responsible for the observed decrease of electron density at the bond critical point detected in AIM studies.

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“…Three different geometries were used as the results appeared to be strongly geometry dependent. Two of these geometries are experimental, 71,72 while the third was a BP-optimized geometry of ref 70 (Table 6, row 9), which was also used in unpublished ∆SCF test calculations. 73 Further technical details concern the convergence of the SCF procedure, the numerical integration accuracy, the criterion for neglecting tails of functions in regions of space where they are close to zero, the convergence of the iterative procedure for solving the excitation energy eigenvalue equation (eq 2), and the criterion for the orthonormality of the trial vectors in this procedure.…”

Section: Technical Details Of the Calculationmentioning

confidence: 99%

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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On the Molecular Structure of Dimanganese Decarcarbonyl, Mn2(CO)10.

Cited by 51 publications

References 0 publications

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

Chemical structures from the analysis of domain‐averaged fermi holes. Nature of the MnMn bond in bis(pentacarbonylmanganese)

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

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On the Molecular Structure of Dimanganese Decarcarbonyl, Mn2(CO)10.

Cited by 51 publications

References 0 publications

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)5−CO and (CO)5Mn−Mn(CO)5

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)5−CO and (CO)5Mn−Mn(CO)5

Chemical structures from the analysis of domain‐averaged fermi holes. Nature of the MnMn bond in bis(pentacarbonylmanganese)

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

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Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

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