Journal ArticleDOI
Experimental X-ray Charge Density Studies on the Binary Carbonyls Cr(CO)6, Fe(CO)5, and Ni(CO)4
Louis J. Farrugia,Cameron Evans +1 more
TLDR
A detailed comparison between the experimental results and theoretical results from previous work and from gas-phase and periodic DFT/B3LYP calculations shows excellent agreement, both on a qualitative and quantitative level.Abstract:
The experimental charge densities in the binary carbonyls Cr(CO)6 (1), Fe(CO)5 (2), and Ni(CO)4 (3) have been investigated on the basis of high-resolution X-ray diffraction data collected at 100 K. The nature of the metal−ligand interactions has been studied by means of deformation densities and by topological analyses using the Atoms in Molecules (AIM) approach of Bader. A detailed comparison between the experimental results and theoretical results from previous work and from gas-phase and periodic DFT/B3LYP calculations shows excellent agreement, both on a qualitative and quantitative level. An examination of the kappa-restricted multipole model (KRMM) for Cr(CO)6, using theoretically derived structure factors, showed it to provide a somewhat worse fit than a model with freely refined κ‘ values. The experimental atomic graphs for the metal atoms in 2 and 3 were found to be dependent on the multipole model used for that atom. In the case of compound 2, restriction of the multipole populations according t...read more
Citations
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Journal ArticleDOI
The QTAIM approach to chemical bonding between transition metals and carbocyclic rings: a combined experimental and theoretical study of (η5-C5H5)Mn(CO)3, (η6-C6H6)Cr(CO)3, and (E)-{(η5-C5H4)CF=CF(η5- C5H4)}(η5-C5H5)2Fe2
TL;DR: The QTAIM indicators clearly demonstrate that for the n-hapto (eta(n)-C(n)H(n))M unit, there is generally a very similar level of chemical bonding for all M-C(ring) interactions, as expected on the basis of chemical experience.
Journal ArticleDOI
Role of Inner- and Outer-Sphere Bonding in the Sensitization of EuIII-Luminescence Deciphered by Combined Analysis of Experimental Electron Density Distribution Function and Photophysical Data
TL;DR: The outcome of this study is that specific interionic interactions which are usually not considered in theoretical calculations or in the interpretation of luminescent properties play an important role in the sensitization of the Eu luminescence.
Journal ArticleDOI
Chemical Bonds without “Chemical Bonding”? A Combined Experimental and Theoretical Charge Density Study on an Iron Trimethylenemethane Complex
TL;DR: High-resolution X-ray diffraction data, in conjunction with DFT(B3LYP) quantum calculations, have been used in a QTAIM analysis of the charge density in the trimethylenemethane (TMM) complex Fe(eta(4)-C[CH(2)](3))(CO)(3).
Journal ArticleDOI
How π back-donation quantitatively controls the CO stretching response in classical and non-classical metal carbonyl complexes
Giovanni Bistoni,Sergio Rampino,Nicola Scafuri,Gianluca Ciancaleoni,Daniele Zuccaccia,Leonardo Belpassi,Francesco Tarantelli +6 more
TL;DR: It is definitively show that the CO stretching response to metal coordination is driven exclusively by π polarization, which quantitatively correlates with π back-donation and changes in CO bond length and frequency.
Journal ArticleDOI
Analysis of electron density distributions from subsystem density functional theory applied to coordination bonds
TL;DR: In this article, the electron density topologies from a subsystem approach to density-functional theory (DFT) for subsystems connected by coordination bonds are investigated, and reasonable results can be obtained for weak dative bonds as in H 3 N⋯-BH 3 or for bonds with a rather ionic character as in TiCl 4.
References
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Journal ArticleDOI
Self-Consistent Equations Including Exchange and Correlation Effects
Walter Kohn,L. J. Sham +1 more
TL;DR: In this paper, the Hartree and Hartree-Fock equations are applied to a uniform electron gas, where the exchange and correlation portions of the chemical potential of the gas are used as additional effective potentials.
Book ChapterDOI
Processing of X-ray diffraction data collected in oscillation mode
Zbyszek Otwinowski,Wladek Minor +1 more
TL;DR: The methods presented in the chapter have been applied to solve a large variety of problems, from inorganic molecules with 5 A unit cell to rotavirus of 700 A diameters crystallized in 700 × 1000 × 1400 A cell.
Journal ArticleDOI
ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI)
TL;DR: L Lists of software presented and~or reviewed in the Journal of Applied Crystallography are available on the World Wide Web at the above address, together with information about the availability of the software where this is known.
Journal ArticleDOI
WinGX suite for small-molecule single-crystal crystallography
TL;DR: The category Computer Program Abstracts provides a rapid means of communicating up-to-date information concerning both new programs or systems and signi®cant updates to existing ones.
Book
Density-functional theory of atoms and molecules
TL;DR: In this paper, a review of current studies in density functional theory and density matrix functional theory is presented, with special attention to the possible applications within chemistry, including the concept of an atom in a molecule, calculation of electronegativities from the Xα method, pressure, Gibbs-Duhem equation, Maxwell relations and stability conditions.