A Full Topological Analysis of Unstable and Metastable Bond Critical Points

Miorelli, Jonathan; Wilson, Timothy; Morgenstern, Amanda; Jones, Travis E.; Eberhart, Mark E.

doi:10.1002/cphc.201402641

Cited by 3 publications

(3 citation statements)

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“…And the union of irreducible bundles sharing a common bond CP gives rise to the bond bundle-a partitioning of the charge density into unique zero flux surface-bounded volumes, each of which contains a single bond path and bond CP. Bond bundles recover traditional bond properties like bond order [14,15], and address issues like spurious bond CPs which have been shown to have tiny bond orders [16].…”

Section: Introductionmentioning

confidence: 99%

Quantum theory of atoms in molecules in condensed charge density space

Wilson

Eberhart

2019

Can. J. Chem.

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By leveraging the fundamental doctrine of The Quantum Theory of Atoms in Molecules-the partitioning of the electron charge density (ρ) into regions bounded by surfaces of zero fluxwe map the gradient field of ρ onto a 2D space called the gradient bundle condensed charge density (P). The topology of P appears to correlate with regions of chemical significance in ρ. The bond wedge is defined as the image in ρ of the basin of attraction in P, analogous to the Bader atom, which is the basin of attraction in ρ. A bond bundle is defined as the union of bond wedges that share interatomic surfaces. We show that maxima in P typically map to bond paths in ρ, though this is not necessarily always true. This observation addresses many of the concerns regarding the chemical significance of bond critical points and bond paths in The Quantum Theory of Atoms in Molecules.

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Section: Introductionmentioning

confidence: 99%

Quantum theory of atoms in molecules in condensed charge density space

Wilson

Eberhart

2019

Can. J. Chem.

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“…Since the physical properties of a system strongly depend on its microscopic features, such a fundamental study could provide useful tools to explore and characterize other physical aspects of a-Si like its mechanical and electronic properties. The Bader's analyzing has been successfully used to study or illustrate many condensed matter phenomena; such as magnetic, structural or crystalline-amorphous phase transitions [18,19], band structure properties [20], dynamical softening and structural stability [21][22][23], exploring the effects of vacancies, defects, and doping in crystalline and amorphous materials [24], etc.…”

Section: Introductionmentioning

confidence: 99%

Bonding properties of amorphous silicon and quantum confinement in the mixed phases of silicon nano slabs

Nourbakhsh

Akbarzadeh

2019

Solar Energy

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On the basis of density functional calculations and using Bader's atom in molecule theory, this article presents quantitative microscopic analyses on the bonding properties of amorphous silicon (a-Si) which could reflect in the observable mechanical and electronic behaviors of this material. In addition, the occurrence and strength of quantum confinement of charge carriers in a composition of silicon crystal nano slabs (SiNSs) embedded in hydrogenated a-Si (a-Si:H) semiconductor are studied. It is shown that the strongest confinement effect happens for Si slabs limited in [100] direction. The band gap tunability with the width of SiNSs is exhibited and a scaling law is investigated for the size dependent behavior of energy states. It is demonstrated and argued why in these systems the confinement of holes is stronger than electron confinement. The computational methodology used to passivate a-Si defects by hydrogen is also detailed.

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“…Additionally, this picture is still imperfect, as critical points are but a single and incomplete characteristic of the charge density's gradient field, rr(r). 9 Accordingly, here we explore the response of the charge density's full gradient field to a perturbation. Our hope is that the understanding resulting from this line of investigation will allow for a closer marriage between the density based electron pushing schemes and the fundamental properties of electron response that can now be investigated using both theoretical and experimental techniques.…”

Section: Introductionmentioning

confidence: 99%

The influence of zero-flux surface motion on chemical reactivity

Morgenstern

Miorelli

et al. 2016

Phys. Chem. Chem. Phys.

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Visualizing and predicting the response of the electron density, ρ(r), to an external perturbation provides a portion of the insight necessary to understand chemical reactivity. One strategy used to portray electron response is the electron pushing formalism commonly utilized in organic chemistry, where electrons are pictured as flowing between atoms and bonds. Electron pushing is a powerful tool, but does not give a complete picture of electron response. We propose using the motion of zero-flux surfaces (ZFSs) in the gradient of the charge density, ∇ρ(r), as an adjunct to electron pushing. Here we derive an equation rooted in conceptual density functional theory showing that the movement of ZFSs contributes to energetic changes in a molecule undergoing a chemical reaction. Using a substituted acetylene, 1-iodo-2-fluoroethyne, as an example, we show the importance of both the boundary motion and the change in electron counts within the atomic basins of the quantum theory of atoms in molecules for chemical reactivity. This method can be extended to study the ZFS motion between smaller gradient bundles in ρ(r) in addition to larger atomic basins. Finally, we show that the behavior of ∇ρ(r) within atomic basins contains information about electron response and can be used to predict chemical reactivity.

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A Full Topological Analysis of Unstable and Metastable Bond Critical Points

Cited by 3 publications

References 40 publications

Quantum theory of atoms in molecules in condensed charge density space

Quantum theory of atoms in molecules in condensed charge density space

Bonding properties of amorphous silicon and quantum confinement in the mixed phases of silicon nano slabs

The influence of zero-flux surface motion on chemical reactivity

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