On the calculation of bonding energies by the Hartree Fock Slater method

Ziegler, Tom; Rauk, Arvi

doi:10.1007/bf02401406

Cited by 2,233 publications

(925 citation statements)

References 16 publications

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“…The natural orbitals for the chemical valence (NOCV) analysis, [21] supported by the extended transition state (ETS) Ziegler-Rauk bond-energy decomposition scheme, [22] fragments. The analysis was performed with the Amsterdam Density Functional (ADF) software package [23] with the Becke-Perdew exchange-correlation functional [15] and the TZP basis sets without afrozen core approximation for all elements.…”

Section: à4mentioning

confidence: 99%

Chelate‐Thiolate‐Coordinate Ligands Modulating the Configuration and Electrochemical Property of Dinitrosyliron Complexes (DNICs)

Yeh

Lin

Liu

et al. 2015

Chemistry A European J

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As opposed to the reversible redox reaction ({Fe(NO)2 }(10) reduced-form DNIC [(NO)2 Fe(S(CH2 )3 S)](2-) (1)⇌{Fe(NO)2 }(9) oxidized-form [(NO)2 Fe(S(CH2 )3 S)](-) ), the chemical oxidation of the {Fe(NO)2 }(10) DNIC [(NO)2 Fe(S(CH2 )2 S)](2-) (2) generates the dinuclear {Fe(NO)2 }(9) -{Fe(NO)2 }(9) complex [(NO)2 Fe(μ-SC2 H4 S)2 Fe(NO)2 ](2-) (3) bridged by two terminal [SC2 H4 S](2-) ligands. On the basis of the Fe K-edge pre-edge energy and S K-edge XAS, the oxidation of complex 1 yielding [(NO)2 Fe(S(CH2 )3 S)](-) is predominantly a metal-based oxidation. The smaller S1-Fe1-S2 bond angle of 94.1(1)° observed in complex 1 (S1-Fe1-S2 88.6(1)° in complex 2), compared to the bigger bond angle of 100.9(1)° in the {Fe(NO)2 }(9) DNIC [(NO)2 Fe(S(CH2 )3 S)](-) , may be ascribed to the electron-rich {Fe(NO)2 }(10) DNIC preferring a restricted bite angle to alleviate the electronic donation of the chelating thiolate to the electron-rich {Fe(NO)2 }(10) core. The extended transition state and natural orbitals for chemical valence (ETS-NOCV) analysis on the edt-/pdt-chelated {Fe(NO)2 }(9) and {Fe(NO)2 }(10) DNICs demonstrates how two key bonding interactions, that is, a FeS covalent σ bond and thiolate to the Fe d z 2 charge donation, between the chelating thiolate ligand and the {Fe(NO)2 }(9/10) core could be modulated by the backbone lengths of the chelating thiolate ligands to tune the electrochemical redox potential (E1/2 =-1.64 V for complex 1 and E1/2 =-1.33 V for complex 2) and to dictate structural rearrangement/chemical transformations (S-Fe-S bite angle and monomeric vs. dimeric DNICs).

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Section: à4mentioning

confidence: 99%

Chelate‐Thiolate‐Coordinate Ligands Modulating the Configuration and Electrochemical Property of Dinitrosyliron Complexes (DNICs)

Yeh

Lin

Liu

et al. 2015

Chemistry A European J

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“…It is analogous to a number of manners of cake-cutting. The present study intends to decompose the energy contributions of the conformers using the energy decomposition analysis (EDA) [33,34,35]. Significant work with various methods has been done in this direction for ferrocene.…”

Section: Introductionmentioning

confidence: 99%

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis

2015

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Two very different quantum mechanically based energy decomposition analyses (EDA) schemes are employed to study the dominant energy differences between the eclipsed and staggered ferrocene conformers. One is the extended transition state (ETS) based on the Amsterdam Density Functional (ADF) package and the other is natural EDA (NEDA) based in the General Atomic and Molecular Electronic Structure System (GAMESS) package. It reveals that in addition to the model (theory and basis set), the fragmentation channels more significantly affect the interaction energy terms (ΔE) between the conformers. It is discovered that such an interaction energy can be absorbed into the pre-partitioned fragment channels so that to affect the interaction energies in a particular conformer of Fc. To avoid this, the present study employs a complete fragment channel—the fragments of ferrocene are individual neutral atoms. It therefore discovers that the major difference between the ferrocene conformers is due to the quantum mechanical Pauli repulsive energy and orbital attractive energy, leading to the eclipsed ferrocene the energy preferred structure. The NEDA scheme further indicates that the sum of attractive (negative) polarization (POL) and charge transfer (CL) energies prefers the eclipsed ferrocene. The repulsive (positive) deformation (DEF) energy, which is dominated by the cyclopentadienyle (Cp) rings, prefers the staggered ferrocene. Again, the cancellation results in a small energy residue in favour of the eclipsed ferrocene, in agreement with the ETS scheme. Further Natural Bond Orbital (NBO) analysis indicates that all NBO energies, total Lewis (no Fe) and lone pair (LP) deletion all prefer the eclipsed Fc conformer. The most significant energy preferring the eclipsed ferrocene without cancellation is the interactions between the donor lone pairs (LP) of the Fe atom and the acceptor antibond (BD*) NBOs of all C–C and C–H bonds in the ligand, LP(Fe)-BD*(C–C & C–H), which strongly stabilizes the eclipsed (D5h) conformation by −457.6 kcal·mol−1.

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“…[44][45][46][47] These results are presented in Table 2. At first place, It must be noted that the total interaction 150 energy strongly depends on the nature of the heteroatom and the charge of the anionic {XO 4 } subunit.…”

Section: Energy Decomposition Analysis (Eda)mentioning

confidence: 84%

Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms

2016

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On the calculation of bonding energies by the Hartree Fock Slater method

Cited by 2,233 publications

References 16 publications

Chelate‐Thiolate‐Coordinate Ligands Modulating the Configuration and Electrochemical Property of Dinitrosyliron Complexes (DNICs)

Chelate‐Thiolate‐Coordinate Ligands Modulating the Configuration and Electrochemical Property of Dinitrosyliron Complexes (DNICs)

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis

Density functional study on Keggin heteropolyanions containing fifth period main group heteroatoms

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