Spatial localization of electron pairs in molecules using the Fisher information density

Astakhov, Andrey A.; Tsirelson, Vladimir G.

doi:10.1016/j.chemphys.2014.03.006

Cited by 20 publications

(22 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…PS‐FID describes in a quasi‐classical manner available information about electron momentum at each point of the position space and serves as an effective electron localization descriptor . It is interesting that almost the same quantity (termed as the “local capacitance”) was proposed recently from other considerations and was found to be correlated with electronic polarizability of atoms.…”

Section: Discussionmentioning

confidence: 85%

“…It is significant that harmonically estimated PVD function is closely related to the recently introduced PS‐FID function:

i_{f} (r) = \frac{9 {normalρ}^{2} (r)}{e^{2} Var (p; r)} = \frac{9}{2 m e^{2}} \frac{{normalρ}^{2} (r)}{t_{G B P} (r)} .

…”

Section: Discussionmentioning

confidence: 93%

“…So PVD function (i) is applicable both to finite systems (as molecules or clusters) and to infinite crystals and (ii) is able to qualitatively distinguish between metallic and insulating electronic states in the thermodynamic limit. Finally, similarity between PVD and recently introduced phase‐space‐defined Fisher information density (PS‐FID), the quasi‐classical measure of local information about electron momentum in the position space, is established. Application of the outlined approach for some molecules demonstrates its ability to distinguish different types of chemical bond.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

Astakhov

Tsirelson

2018

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

In this work, the electron organization of many‐electron systems is considered in a context of the linear response theory extending the Kohn‐Resta view on electron localization phenomenon. The variances of the local electronic position and momentum operators are linked via the fluctuation‐dissipation theorem to the optical conductivity tensor, that is, to observable spectroscopic properties. It is demonstrated that the electron position variance density quantifies a degree of electron delocalization in each point of position space and distinguishes between metallic and insulating character of electronic states. The momentum variance density estimates a degree of electron localization and is immediately related to electronic kinetic energy density in the Ghosh‐Berkowitz‐Parr form giving a physical interpretation to the later. We show that electron localization and delocalization phenomena in atoms and molecules can be probed by external electric field. This approach provides new electronic descriptors distinguishing and quantifying chemical bonds of different types.

show abstract

Section: Discussionmentioning

confidence: 85%

“…It is significant that harmonically estimated PVD function is closely related to the recently introduced PS‐FID function:

i_{f} (r) = \frac{9 {normalρ}^{2} (r)}{e^{2} Var (p; r)} = \frac{9}{2 m e^{2}} \frac{{normalρ}^{2} (r)}{t_{G B P} (r)} .

…”

Section: Discussionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

Astakhov

Tsirelson

2018

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…In this context, information theory (IT) has been shown to be advantageous at the moment of inferring the properties of molecular systems, and a number of IT‐founded methodologies and concepts have been proposed in the later years. The information functional theory of Liu and coworkers, the quantum information theory of Nalewajsky, the information‐theoretic ELF (IT‐ELF) of Nalewasjski and coworkers, and the phase‐space Fisher information density (PS‐FID) of Astakhov and Tsirelson can be mentioned as representative examples of the aforementioned methodologies. It is opportune to point out that the latter theories rely on the use of the one‐electron density—obtained from a previously computed Ψ—as the source of information, which is indeed a natural choice considering that IT was designed to deal with probability distributions (see below).…”

Section: Introductionmentioning

confidence: 99%

A review on the information content of the pair density as a tool for the description of the electronic properties in molecular systems

Torres

Rincón

Zambrano

et al. 2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Recent advances on the use of the information content of the pair density to understand bonding and reactivity of molecular systems are presented. Two quantities are described: (1) the information content of the like‐spin exchange‐correlation hole, χ XC, and (2) the information content of the Coulomb hole, χ C, of the like‐spin and the unlike‐spin cases. χ XC is capable of describing the electron structure of molecules on the basis of chemical grounds with astonishing accuracy and provides a clear differentiation of the localization degree of electrons, belonging to different molecular basins. Furthermore, χ XC is used as a tool to get insights in the electronic reorganization occurring along a reaction coordinate. In contrast to χ XC, χ C is observed to concentrate in regions between atomic shells, from which information of nonclassical weak interactions can be obtained. Some relevant problems, in which the application of χ XC in conjunction with χ C would be of great value, are presented.

show abstract

“…Therefore, the different tools have been suggested to locate the regions of electron concentration and depletion. We mention the Laplacian of electron density [37], electron localization function (ELF) [42,43], electron localizability indicator [44,45,46], localized orbital locator [47,48], one-electron potential [49], maximum probability domains [50,51,52], conditional pair density [53], localized electron detector [54,55,56], single exponential decay detector [57,58], information-theoretic ELF [59], steric [60] and Pauli [61] potentials and phasespace Fisher information density [62]. These descriptors play nowadays an important role in the chemical bonding analysis despite some their drawbacks.…”

Section: Introductionmentioning

confidence: 99%

Bonding in molecular crystals from the local electronic pressure viewpoint

2015

Self Cite

View full text Add to dashboard Cite

The spatial distribution of the internal pressure of an electron fluid, which spontaneously arises at the formation of a molecule or a crystal, is linked to the main features of chemical bonding in molecular crystals. The local pressure is approximately expressed in terms of the experimental electron density and its derivatives using the density functional formalism and is applied to identify the bonding features in benzene, formamide and chromium hexacarbonyl. We established how the spatial regions of compression and stretching of the electron fluid in these solids reflect the typical features of chemical bonds of different types. Thus, the internal electronic pressure can serve as a bonding descriptor, which has a clear physical meaning and reveals the specific features of variety of the chemical bonds expressing them in terms of the electron density.

show abstract

Spatial localization of electron pairs in molecules using the Fisher information density

Cited by 20 publications

References 70 publications

Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

A review on the information content of the pair density as a tool for the description of the electronic properties in molecular systems

Bonding in molecular crystals from the local electronic pressure viewpoint

Contact Info

Product

Resources

About