A first step towards quantum energy potentials of electron pairs

Munárriz, Julen; Laplaza, Rubén; Pendás, Ángel Martín; Contreras‐García, Julia

doi:10.1039/c8cp07509c

Cited by 14 publications

(26 citation statements)

References 48 publications

(50 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This class of methods can also have other practical uses, maybe most notably for the design of molecular mechanics force fields. [14,57,58] The explanations offered by EDAs are seldom "chemical explanations" in the sense that interactions are not directly described in terms of "atom in molecules" chemical properties, such as electronegativity, valence, ionic, and covalent radii. The latter properties are determined by the location of the constituent atoms in the periodic table.…”

Section: Bernard Silvi Eduard Matito and Martin Rahmmentioning

confidence: 99%

“…Whereas we have not mentioned all varieties here, most EDAs can provide important pieces of information on chemical interactions. This class of methods can also have other practical uses, maybe most notably for the design of molecular mechanics force fields . The explanations offered by EDAs are seldom “chemical explanations” in the sense that interactions are not directly described in terms of “atom in molecules” chemical properties, such as electronegativity, valence, ionic, and covalent radii.…”

Section: A Few Bars Of Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Nine questions on energy decomposition analysis

Andrés

Ayers

Boto³

et al. 2019

J Comput Chem

120

123

View full text Add to dashboard Cite

The paper collects the answers of the authors to the following questions: Is the lack of precision in the definition of many chemical concepts one of the reasons for the coexistence of many partition schemes? Does the adoption of a given partition scheme imply a set of more precise definitions of the underlying chemical concepts? How can one use the results of a partition scheme to improve the clarity of definitions of concepts? Are partition schemes subject to scientific Darwinism? If so, what is the influence of a community's sociological pressure in the “natural selection” process? To what extent does/can/should investigated systems influence the choice of a particular partition scheme? Do we need more focused chemical validation of Energy Decomposition Analysis (EDA) methodology and descriptors/terms in general? Is there any interest in developing common benchmarks and test sets for cross‐validation of methods? Is it possible to contemplate a unified partition scheme (let us call it the “standard model” of partitioning), that is proper for all applications in chemistry, in the foreseeable future or even in principle? In the end, science is about experiments and the real world. Can one, therefore, use any experiment or experimental data be used to favor one partition scheme over another? © 2019 Wiley Periodicals, Inc.

show abstract

Section: Bernard Silvi Eduard Matito and Martin Rahmmentioning

confidence: 99%

Section: A Few Bars Of Introductionmentioning

confidence: 99%

Nine questions on energy decomposition analysis

Andrés

Ayers

Boto³

et al. 2019

J Comput Chem

120

123

View full text Add to dashboard Cite

show abstract

“…The methodological aspects of the conjoined ELF-BCM have been extensively covered elsewhere, 30 and shown to be valid for covalent bonds. It must be noted that the charge equalization between Z and q may not be sufficient in the context of the ELF-BCM, as in general core populations are constant with respect to the chemical environment but bond population q may migrate towards lone pairs or other bonds in polyatomic systems which are not directly involved in the bonding interaction.…”

Section: Approximate Energy Models Of Covalent Bondsmentioning

confidence: 99%

A Bond Charge Model Ansatz for Intrinsic Bond Energies: Application to C–C Bonds

2019

Self Cite

View full text Add to dashboard Cite

A simple Bond Charge Model is proposed to predict intrinsic bond energies. Model parameters can be derived from the topology of the Electron Localization Function and optimized geometries through classic considerations. Results for carbon-carbon covalent bonds are shown to be very accurate in different chemical environments. Insight can be extracted from the application of the model due to its elementary construction and simple mathematical formulation. The remarkable robustness of the fitted model highlights how different Density Functional Approximations relate geometries, densities and energies.

show abstract

Section: Introductionmentioning

confidence: 99%

“…The development of simple modelst hat facilitateareliable predictiona nd rationalization of molecular structures and properties is of great importance in currentc hemical research. [1,2] In this regard,agood example of the predictive charactero fasimple energy model is the well-known valenceshell electron-pair repulsion (VSEPR)t heory.S pecifically,i t allows molecularg eometries to be predicted in terms of the repulsion between electronp airs. [3] This theory hasp rovent o work well form ain-group-baseds ystems, [4] with only some exceptions,e specially for complexes bearing ad 0 central atom.…”

Section: Introductionmentioning

confidence: 99%

Valence‐Shell Electron‐Pair Repulsion Theory Revisited: An Explanation for Core Polarization

Munárriz

Calatayud

Contreras‐García

2019

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Valence‐shell electron‐pair repulsion (VSEPR) theory constitutes one of the pillars of theoretical predictive chemistry. It was proposed even before the advent of the concept of “spin”, and it is still a very useful tool in chemistry. In this article we propose an extension of VSEPR theory to understand the core structure and predict core polarization in the main‐group elements. We show from first principles (Electron Localization Function analysis) how the inner‐ and outer‐core shells are organized. In particular, electrons in these regions are structured following the shape of the dual polyhedron of the valence shell (3rd period) or the equivalent polyhedron (4th and 5th periods). We interpret these results in terms of “hard” and “soft” core character. All the studied systems follow this trend, providing a framework for predicting electron distribution in the core. We also show that lone pairs behave as “standard ligands” in terms of core polarization. The predictive character of the model was tested by proposing the core polarization in different systems not included in the original set (such as XeF4 and [Fe(CN)6]3−) and checking the hypothesis by means of a posteriori calculations. From the experimental point of view, the extension of VSEPR to the core region has consequences for current crystallography research. In particular, it explains the core polarization revealed by high resolution X‐ray experiments.

show abstract

A first step towards quantum energy potentials of electron pairs

Abstract: A first step towards the construction of a quantum force field for electron pairs in direct space is taken.

Cited by 14 publications

References 48 publications

Nine questions on energy decomposition analysis

Nine questions on energy decomposition analysis

A Bond Charge Model Ansatz for Intrinsic Bond Energies: Application to C–C Bonds

Valence‐Shell Electron‐Pair Repulsion Theory Revisited: An Explanation for Core Polarization

Contact Info

Product

Resources

About