Electronic structure of CO—An exercise in modern chemical bonding theory

Frenking, Gernot; Loschen, Christoph; Krapp, Andreas; Fau, Stefan; Strauss, Steven H.

doi:10.1002/jcc.20477

Cited by 124 publications

(136 citation statements)

References 32 publications

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“…All partitioning methods give a negative partial charge at the more electronegative oxygen atom. [44] Another point raised concerned the homolytic and heterolytic EÀPPh 3 bond fission of E-A C H T U N G T R E N N U N G (PPh 3 ) 2 as a criterion for the nature of the bonds. The referee commented that tBuCl is, for example, substituted via a SN1 mechanism which yields a tBu + ion through a heterolytic bond fission, and does this imply a heterolytic bond?…”

Section: Resultsmentioning

confidence: 99%

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Takagi

Tonner

Frenking

2012

Chemistry A European J

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Quantum-chemical calculations at the BP86/TZVPP level have been carried out for the heavy Group 14 homologues of carbodiphosphorane E(PPh(3))(2), where E=Si, Ge, Sn, Pb, which are experimentally unknown so far. The results of the theoretical investigation suggest that the tetrelediphosphoranes E(PPh(3))(2) (1E) are stable compounds that could become isolated in a condensed phase. The molecules possess donor-acceptor bonds Ph(3)P→E←PPh(3) to a bare tetrele atom E, which retains its four valence electrons as two electron lone pairs. The analysis of the bonding situation and the calculation of the chemical reactivity indicate that the molecules 1E belong to the class of divalent E(0) compounds (ylidones). All molecules 1C-1Pb have very large first but also very large second proton affinities, which distinguishes them from the N-heterocyclic carbene homologues, in which the donor atom is a divalent E(II) species that possesses only one electron lone pair. Compounds 1E are powerful double donors that strongly bind Lewis acids such as BH(3) and AuCl in the complexes 1E(BH(3))(n) and 1E(AuCl)(n) (n=1, 2). The bond dissociation energies (BDEs) of the second BH(3) and AuCl molecules are only slightly less than the BDE of the first BH(3) and AuCl. The results of this work are a challenge for experimentalists.

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Section: Resultsmentioning

confidence: 99%

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Takagi

Tonner

Frenking

2012

Chemistry A European J

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“…Sophisticated quantum-chemical calculations are able to reproduce the experimental CO dipole moment [199,200] and provide an explanation for this unusual situation [201][202][203]. The dipole moment is a vector quantity, and the shape of the electron distribution may be more important in the determination of its sign than the scalar atomic charges.…”

Section: A-1 Dipole Moment and Exceeding The 8−n Rulementioning

confidence: 94%

“…Thus, according to ref. [203], it is the highly asymmetrical partitioning of the electron cloud around carbon, and in particular the placement of the lone pair, that results in carbon being the negative end of the dipole moment while, at the same time, carrying a positive partial charge compliant with EN. 21 Calculations show a similar situation for BF [201] and NF [202], which, however, are unstable [204,205].…”

Section: A-1 Dipole Moment and Exceeding The 8−n Rulementioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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“…10 They are commonly used to determine bond polarity and ionic/covalent character of bonding although charge is a scalar quantity which does not carry information about the charge distribution; this can significantly alter interpretation. 11 A popular method in surface science is the analysis of density of states (DOS) and partial DOS (pDOS) as more easily accessible representation of the band structure. 12 Closely related, an analysis of bonding and antibonding character of orbitals in an energy interval of a DOS/pDOS can be carried out with the crystal orbital overlap population (COOP) 13 and the related crystal orbital Hamilton population (COHP) method.…”

Section: Introductionmentioning

confidence: 99%

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

Raupach

Tonner

2015

The Journal of Chemical Physics

110

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The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H2 on M(001), M = Pd, Cu), and semiconducting (CO and C2H2 on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.

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Electronic structure of CO—An exercise in modern chemical bonding theory

Cited by 124 publications

References 32 publications

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

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Electronic structure of CO—An exercise in modern chemical bonding theory

Cited by 124 publications

References 32 publications

Carbodiphosphorane Analogues E(PPh3)2 with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh3)2 with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

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Product

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Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design