Decomposition of deformation density into orbital components

Pakiari, A.H.; Fakhraee, Sara; Azami, S.M.

doi:10.1002/qua.21453

Cited by 9 publications

(7 citation statements)

References 16 publications

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“…These functions are conceptually similar to the deformation natural orbitals (DNOs) 38 or the natural orbitals for chemical valence (NOCVs), [39][40][41] employed to study the bond formation in complexes and covalent intramolecular interactions, respectively, and the natural transition orbitals, 42 extensively applied to analyze the orbital contributions in electronic transitions. In this case of EDOs, they represent the eigenchannels for the electrically induced electron transport in molecules.…”

Section: Molecular Electric Conductance From Electron Deformation Orbmentioning

confidence: 99%

Anti-ohmic single molecule electron transport: is it feasible?

et al. 2019

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Section: Molecular Electric Conductance From Electron Deformation Orbmentioning

confidence: 99%

Anti-ohmic single molecule electron transport: is it feasible?

et al. 2019

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“…The EDOs defined by eq. (2) are conceptually similar to the deformation natural orbitals (DNOs) [32] obtained by diagonalization of the deformation density matrix associated to complex formation, the natural orbitals for chemical valence (NOCVs) [33][34][35] obtained by diagonalization of the deformation density matrix associated to the bond formation and the natural transition orbitals [36] associated to an electronic transition and obtained from a corresponding orbital transformation [37] of the transition density matrix.…”

Section: Theoretical Developmentsmentioning

confidence: 99%

Analyzing the electric response of molecular conductors using “electron deformation” orbitals and occupied‐virtual electron transfer

Mandado

Ramos‐Berdullas

2014

J Comput Chem

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The concept of "electron deformation orbitals" (EDOs) is used to investigate the electric response of conducting metals and oligophenyl chains. These orbitals and their eigenvalues are obtained by diagonalization of the deformation density matrix (difference between the density matrices of the perturbed and unperturbed systems) and can be constructed as linear combinations of the unperturbed molecular orbitals within "frozen geometry" conditions. This form of the EDOs allows calculating the part of the electron deformation density associated to an effective electron transfer from occupied to virtual orbitals (valence to conduction band electron transfer in the band model of conductivity). It is found that the "electron deformation" orbitals pair off, displaying the same eigenvalue but opposite sign. Each pair represents an amount of accumulation/depletion of electron charge at different molecular regions. In the oligophenyl systems investigated only one pair contributes effectively to the charge flow between molecular ends, resulting from the promotion of electrons from occupied orbitals to close in energy virtual orbitals of appropriate symmetry and overlapping. Analysis of this pair along explains the differences in conductance of olygophenyl chains based on phenyl units.

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“…[50][51][52][53][54] In this scheme a few eigenfunctions (NOCV) of the deformation density matrix (∆P) is used to describe bond formation of the molecules from atoms or fragments in a compact form. [50][51][52][53][54]56 The related eigenvalues can in addition be used as valence indices as well as a measure of the change in the density associated with bond formation. However, the NOVC scheme [50][51][52][53][54] does not provide information about the energetics related to the charge rearrangement.…”

Section: Introductionmentioning

confidence: 99%

A Combined Charge and Energy Decomposition Scheme for Bond Analysis

Mitoraj

Michalak

Ziegler

2009

J. Chem. Theory Comput.

1,481

1,504

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2007, 13, 347 ]. The ETS-NOCV charge and energy decomposition scheme based on the Kohn-Sham approach makes it not only possible to decompose the deformation density, Δρ, into the different components (such as σ, π, δ, etc.) of the chemical bond, but it also provides the corresponding energy contributions to the total bond energy. Thus, the ETS-NOCV scheme offers a compact, qualitative, and quantitative picture of the chemical bond formation within one common theoretical framework. Although, the ETS-NOCV approach contains a certain arbitrariness in the definition of the molecular subsystems that constitute the whole molecule, it can be widely used for the description of different types of chemical bonds. The applicability of the ETS-NOCV scheme is demonstrated for single (H3X-XH3, for X = C, Si, Ge, Sn) and multiple (H2X═XH2, H3CX≡XCH3, for X = C, Ge) covalent bonds between main group elements, for sextuple and quadruple bonds between metal centers (Cr2, Mo2, W2, [Cl4CrCrCl4](4-)), and for double bonds between a metal and a main group element ((CO)5Cr═XH2, for X = C, Si, Ge, Sn). We include finally two applications involving hydrogen bonding. The first covers the adenine-thymine base pair and the second the interaction between C-H bonds and the metal center in the alkyl complex.

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Decomposition of deformation density into orbital components

Cited by 9 publications

References 16 publications

Anti-ohmic single molecule electron transport: is it feasible?

Anti-ohmic single molecule electron transport: is it feasible?

Analyzing the electric response of molecular conductors using “electron deformation” orbitals and occupied‐virtual electron transfer

A Combined Charge and Energy Decomposition Scheme for Bond Analysis

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