An MO-theoretical Interpretation of the Nature of Chemical Reactions. I. Partitioning Analysis of the Interaction Energy

FukuiKenichi,; FujimotoHiroshi,

doi:10.1246/bcsj.41.1989

Cited by 167 publications

(47 citation statements)

References 29 publications

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“…(26) and (31), the expressions for ES and EX interaction energies are completely identical to those of Murrel-Fueno et al [ l ] and Fukui et al [2]. The first term of eq.…”

Section: Occsupporting

confidence: 59%

A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

Kitaura

Morokuma

1976

Int J of Quantum Chemistry

2,018

1,344

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AbstractsA new method is proposed for the analysis of components of molecular interaction energy within the Hartree-Fock approximation. The liartree-Fock molecular orbitals of the isolated molecules are used as the basis for the construction of Fock matrix of the supermolecule. Then certain blocks of this matrix are set to zero subject to specify boundary conditions of the supermolecule molecular orbitals, and the resultant matrix is diagonalized iteratively to obtain the desired energy components. This method can be considered as an extension of our previous method, but has an advantage in the explicit definition of the charge transfer energy, placing it on an equal footing with the exchange and polarization terms. The new method is compared with existing perturbation methods, and is also applied to the energy and electron density decomposition of (H,O),.On propose une nouvelle mkthode pour analyser les composantes de I'energie d'interaction moliculaire dans le cadre de I'approximation Hartree-Fock. Les orbitales moleculaires des molkcules isolkes sont utiliskes comme base pour construire la matrice de Fock de la supermolecule. Certains blocs de cette matrice sont mis egaux a zero selon des conditions aux limites spkcifiques et la matrice rksultante est diagonalisee d'une faqon iterative pour obtenir les composantes cherchkes. Cette mkthode-ci peut itre considerke comme une extension de notre mkthode antkrieure mais elle a un avantage dans la definition explicite de I'energie de transfert de charge, qui est mise ici au mime rang que les termes d'kchange et de polarisation. La nouvelle mkthode est comparke aux methodes de perturbation traditionelles. Elle a dtk appliquee a la decomposition de I'energie et de la densite ilectronique de (H20)2.Es wird eine neue Methode fur die Analyse der Komponenten der molekularen Wechselwirkungsenergie in der Hartree-Fock-Naherung vorgeschlagen. Die Hartree-FockOrbitale der freien Molekiile werden verwendet als Basis fur die Konstruktion der Fock' schen Matrix des Supermolekiils. Gewisse Blocke dieser Matrix werden nach spezifischen Grenzbedingungen gleich Null gesetzt, und die resultierende Matrix wird in einer iterativen Weise diagonalisiert um die gewiinschten Energiekomponenten zu geben. Diese Methode kann als eine Ergazung unserer friiheren Methode betrachtet werden. Sie hat aber einen Vorteil in der expliziten Definition der Ladungsuberfuhrungsenergie, die hier an denselben Niveau wie die Austausch-und Polarisationsglieder hingestellt wird. Die neue Methode wird mit existierenden Storungsmethoden verglichen. Sie wird auf die Zerlegung der Energie und der Elektronendichte von (H20), angewandt.

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“…(26) and (31), the expressions for ES and EX interaction energies are completely identical to those of Murrel-Fueno et al [ l ] and Fukui et al [2]. The first term of eq.…”

Section: Occsupporting

confidence: 59%

A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

Kitaura

Morokuma

1976

Int J of Quantum Chemistry

2,018

1,344

View full text Add to dashboard Cite

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“…Finally, it is important to mention that several methods for partitioning the energy of interacting systems have been proposed in the literature [17][18][19][20][21][22][23][24][25][26][27]. They are based on perturbational expansions [17][18][19][20], molecular fragment partition [21], or the use of reduced density or pair density matrices [22][23][24][25][26][27]. However, most of these expansions rely on monoconfigurational Hartree-Fock (HF) formalism and, in general, the associated energy partition scheme, cannot be interpreted as a many-body expansion as in the present approach.…”

Section: Introductionmentioning

confidence: 99%

Many‐body energy decomposition analysis of cooperativity in hydrogen fluoride clusters

Rincón

Almeida

Garcı́a-Aldea

2004

Int J of Quantum Chemistry

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ABSTRACT:This article studies the cooperativity present in hydrogen fluoride clusters, (FH) n , by means of a many-body decomposition of the binding energy. With the aim of quantifying how the results depend on the calculation level, the partition was performed from dimer to hexamer at the RHF, MP2, and density functional (B3LYP) levels, and for the heptamer and octamer at the RHF and B3LYP levels, using a 6-31ϩϩG(d, p) basis set in all cases. We obtain that, for a proper representation of the cooperative effects in hydrogen fluoride, at least the inclusion of the three-body terms is fundamental. The contributions are found to be underestimated at the RHF level and overestimated at the B3LYP level, with respect to the MP2 results.

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“…The general acid-base reaction can be treated by perturbation theory, as pioneered by Dewar (9) and Fukui and Fujimoto (10). The three main bonding interactions between closed-shell molecules or ions are (i) electrostatic, (ii) delocalization, and (iii) polarization.…”

mentioning

confidence: 99%

Absolute electronegativity and hardness correlated with molecular orbital theory

Pearson

1986

Proc. Natl. Acad. Sci. U.S.A.

1,448

512

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The concepts of absolute electronegativity, X, and absolute hardness, g, are incorporated into molecular orbital theory. A graphic and concise definition of hardness is given as twice the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Useful correlations can now be made between chemical behavior, visible-UV absorption spectra, optical polarizability, ionization potentials, and electron affinities.The concepts of absolute electronegativity, X, and absolute hardness, 71, have recently been introduced (1,2 [2]The value of X, equal to 4 eV, is shown with changed sign as a dashed horizontal line in Fig. 1 (see ref. 7). It falls exactly at the energy midpoint between the HOMO and the LUMO. Negative X is equal to the electronic chemical potential, A (1).The value of q, equal to 6 eV, is shown as a vertical dashed line. The energy gap between the HOMO and LUMO is equal to 227.The above refers to a system where the HOMO is filled. Radicals, where the frontier orbital (SOMO) is half-filled, are somewhat different. Fig. 1 shows the orbital energy diagram for a radical where I = 10 eV and A = +2 eV. The energy of the SOMO (equal to -10 eV), X (= 6 eV), and q (= 4 eV) are shown on the figure. The (unknown) energy of the LUMO plays no role. The quantity (I -A) = 227 is just the mean repulsion energy of two electrons in the SOMO (8).Apart from the radical cases, it would appear that Fig. 1 Whether a given molecule is a Lewis acid or a base is determined by its X value. Large X values characterize acids and small X values are found for bases. For any two molecules, electrons will be partially transferred from the one of low X to that of high X (electrons flow from high chemical potential to low chemical potential). In Fig. 1 the radical will act as a Lewis acid toward the molecule.The general acid-base reaction can be treated by perturbation theory, as pioneered by Dewar (9) and Fukui and Fujimoto (10). The three main bonding interactions between closed-shell molecules or ions are (i) electrostatic, (ii) delocalization, and (iii) polarization. Delocalization occurs by partial transfer of electrons from the filled orbitals of one molecule to the empty orbitals of the second. For molecules of similar electronegativities, it will occur in both directions.An approximate expression for the delocalization energy, considering only the frontier orbitals, is given by(A1 -I2) (A2 -I) [3] where the f factors are exchange integrals of the perturbation Hamiltonian over the interacting 4Os. Clearly, the energy lowering is greater if A is large for both molecules and I is small. This means that both energy gaps should be small for best bonding, or both molecules should be soft. This is part of the reason for the principle of hard and soft acids and bases (3). Another contribution to the added stability of a soft acid-soft base complex comes from the mutual polarization effect. A small energy gap favors easy polarization for both molecules. Note, however, 8440The publication c...

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An MO-theoretical Interpretation of the Nature of Chemical Reactions. I. Partitioning Analysis of the Interaction Energy

Cited by 167 publications

References 29 publications

A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

Many‐body energy decomposition analysis of cooperativity in hydrogen fluoride clusters

Absolute electronegativity and hardness correlated with molecular orbital theory

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