Electron Density Distribution In Molecules Research Articles

Testing of Exchange-Correlation Functionals of DFT for a Reliable Description of the Electron Density Distribution in Organic Molecules

Researchers carrying out calculations using the DFT method face the problem of the correct choice of the exchange-correlation functional to describe the quantities they are interested in. This article deals with benchmark calculations aimed at testing various exchange-correlation functionals in terms of a reliable description of the electron density distribution in molecules. For this purpose, 30 functionals representing all rungs of Jacob's Ladder are selected and then the values of some QTAIM-based parameters are compared with their reference equivalents obtained at the CCSD/aug-cc-pVTZ level of theory. The presented results show that the DFT method undoubtedly has the greatest problems with a reliable description of the electron density distribution in multiple strongly polar bonds, such as C=O, and bonds associated with large electron charge delocalization. The performance of the tested functionals turned out to be unsystematic. Nevertheless, in terms of a reliable general description of QTAIM-based parameters, the M11, SVWN, BHHLYP, M06-HF, and, to a slightly lesser extent, also BLYP, B3LYP, and X3LYP functionals turned out to be the worst. It is alarming to find the most popular B3LYP functional in this group. On the other hand, in the case of the electron density at the bond critical point, being the most important QTAIM-based parameter, the M06-HF functional is especially discouraged due to the very poor description of the C=O bond. On the contrary, the VSXC, M06-L, SOGGA11-X, M06-2X, MN12-SX, and, to a slightly lesser extent, also TPSS, TPSSh, and B1B95 perform well in this respect. Particularly noteworthy is the overwhelming performance of double hybrids in terms of reliable values of bond delocalization indices. The results show that there is no clear improvement in the reliability of describing the electron density distribution with climbing Jacob's Ladder, as top-ranked double hybrids are also, in some cases, able to produce poor values compared to CCSD.

Assessment of the flotation activity of reagents in terms of the hydrogen bond energy in molecular complexes with active sites of the coal surface

The hydrogen bond energy of molecular complexes between a flotation reagent and coal’s organic mass is calculated for the first time. The electron density distribution in molecules of 2-methyl-1,3-dioxane and 2-methyl-1,3-dioxa-2-silacyclohexane is determined. It is shown that the silicon atom in the molecule of 2-methyl-1,3-dioxa-2-silacyclohexane increases the electron density at oxygen atoms from −0.279 to −0.424 and −0.432 in positions 1 and 3 of the molecule, respectively. This increases the hydrogen bond energy of the reagent in molecular complexes with water and model compounds of the coal’s organic mass. In molecular complexes of 2-methyl-1,3-dioxa-2-silacyclohexane with model compounds of the coal’s organic mass, the hydrogen bond energy is considerably higher than in corresponding complexes of 2-methyl-1,3-dioxane. As a result, the adsorption of 2-methyl-1,3-dioxa-2-silacyclohexane on the coal surface is 35–45% greater than for 2-methyl-1,3-dioxane. Consequently, the coal grains become more hydrophobic, and their flotation is improved. With the same consumption of reagents, the use of 2-methyl-1,3-dioxa-2-silacyclo-hexane rather than 2-methyl-1,3-dioxane increases the concentrate yield and reduces the losses of the coal’s organic mass with the wastes. Analogous flotation properties of coal are found for other cyclic acetals and their silicon analogs. Experimental data confirm that the hydrogen bond energy in complexes between the flotation reagent and the coal’s organic mass may be used to assess its effectiveness.

Symmetry interplay in Brownian photomotors: From a single-molecule device to ensemble transport

Unlike most of Brownian motor models in which the state of a point particle is described by a single scalar fluctuating parameter, we consider light-induced dichotomic fluctuations of electron density distributions in an extended molecule moving in the electrostatic periodic potential of a polar substrate. This model implies that the potential energy profiles of two motor states differ substantially and their symmetry is dictated by the interplay between the symmetries of the substrate potential and of molecular electronic states. As shown, a necessary condition for the occurrence of directed motion, the asymmetry of the potential energy profiles, is satisfied for (i) symmetric electron density distributions in molecules on asymmetric substrates and (ii) asymmetric electron density distributions in molecules on symmetric substrates. In the former case, the average velocity of directed motion is independent of molecular orientations and the ensemble of molecules moves as a whole, whereas in the latter case, oppositely oriented molecules move counterdirectionally thus causing the ensemble to diffuse. Using quantum chemical data for a specific organic-based photomotor as an example, we demonstrate that the behavior of molecular ensembles is controllable by switching on/off resonance laser radiation: they can be transported as a whole or separated into differently oriented molecules depending on the ratio of symmetric and antisymmetric contributions to the substrate electrostatic potential and to the molecular electron density distributions.

Can a Dipole-Bound Electron Form a Pseudo-Atom? An Atoms-In-Molecules Study of the Hydrated Electron

Non-nuclear local maxima, or attractors, of electron density are a rare but very interesting feature of the electron density distribution in molecules and solids. Recently, non-nuclear attractors (NNAs) and the corresponding pseudoatoms of electron density have been identified with the quantum theory of atoms in molecules for some anionic clusters formed by several polar solvent molecules and an excess electron bound in either a solvated-electron or dipole-bound fashion. This contribution reports a detailed study of the topology of the electron density for a series of dipole-bound water cluster anions, as calculated with Hartree-Fock, Møller-Plesset perturbation theory, and coupled-cluster methods together with basis sets augmented with extra diffuse basis functions to accommodate the excess electron. For dipole-bound clusters, electron densities obtained with insufficient inclusion of electron correlation effects and tight basis sets feature a well-pronounced pseudoatom due to the excess electron, which ultimately disappears when a higher level of electronic structure theory and a more diffuse basis set are used. On the other hand, for solvated-electron clusters, where the excess electron is surrounded by solvent molecules, the existence of NNAs does not seem to be an artifact of the method employed, but rather a genuine feature of the electron density distribution. Pseudoatoms of electron density thus appear to be an exclusive feature of confined environments and are unlikely to be found on the tip of a cluster dipole or on solid surfaces.

Electron density distribution in molecules of 4-aryl-substituted [2.2]paracyclophanes and regioselectivity of their complexation with Cr(CO)3

Charges on carbon atoms in the molecules of 4-aryl-substituted [2.2]paracyclophanes were estimated and the role of charge control as a kinetic factor in regioselectivity of their complexation with (NH3)3Cr(CO)3 was investigated using electron density distribution analysis by the Bader, Weinhold-Reed (NPA), and Mulliken methods. The most plausible picture of the electron density distribution in substituted [2.2]paracyclophanes was obtained by the Bader method and compared with experimental data on the yields of reaction products. Topological analysis of the electron density distribution in the [2.2]paracyclophane molecule by the Bader method confirmed the existence of a weak antibonding interaction between the stacked benzene rings.

X-Ray Charge Densities and Chemical Bonding

This book deals with the electron density distribution in molecules and solids as obtained experimentally by X-ray diffraction. It is a comprehensive treatment of the methods involved, and the interpretation of the experimental results in terms of chemical bonding and intermolecular interactions. Inorganic and organic solids, as well as metals, are covered in the chapters dealing with specific systems. As a whole, this monograph is especially appealing because of its broad interface with numerous disciplines. Accurate X-ray diffraction intensities contain fundamental information on the charge distribution in crystals, which can be compared directly with theoretical results, and used to derive other physical properties, such as electrostatic moments, the electrostatic potential and lattice energies, which are accessible by spectroscopic and thermodynamic measurements. Consequently, the work will be of great interest to a broad range of crystallographers and physical scientists.

Electron Domains and the VSEPR Model of Molecular Geometry

AbstractThe valence shell electron pair repulsion (VSEPR) model—also known as the Gillespie–Nyholm rules—has for many years provided a useful basis for understanding and rationalizing molecular geometry, and because of its simplicity it has gained widespread acceptance as a pedagogical tool. In its original formulation the model was based on the concept that the valence shell electron pairs behave as if they repel each other and thus keep as far apart as possible. But in recent years more emphasis has been placed on the space occupied by a valence shell electron pair, called the domain of the electron pair, and on the relative sizes and shapes of these domains. This reformulated version of the model is simpler to apply, and it shows more clearly that the Pauli principle provides the physical basis of the model. Moreover, Bader and his co‐workers' analysis of the electron density distribution of many covalent molecules have shown that the local concentrations of electron density (charge concentrations) in the valence shells of the atoms in a molecule have the same relative locations and sizes as have been assumed for the electron pair domains in the VSEPR model, thus providing further support for the model. This increased understanding of the model has inspired efforts to examine the electron density distribution in molecules that have long been regarded as exceptions to the VSEPR model to try to understand these exceptions better. This work has shown that it is often important to consider not only the relative locations and sizes, but also the shapes, of both bonding and lone pair domains in accounting for the details of molecular geometry. It has also been shown that a basic assumption of the VSEPR model, namely that the core of an atom underlying its valence shell is spherical and has no influence on the geometry of a molecule, is normally valid for the nonmetals but often not valid for the metals, including the transition metals. The cores of polarizable metal atoms may be nonspherical because they include nonbonding electrons or because they are distorted by the ligands, and these nonspherical cores may have an important influence on the geometry of a molecule.

Bonded hydrogen and hydrogen bonding in reciprocal space. Simulation of diffraction by a water molecule and dimer

There seems to be increasing interest in the electron density distribution in molecules and crystals. In particular, the effect of polarization due to internal fields in condensed matter is studied. X-ray diffraction data can contribute to the knowledge required. As the effects of polarization on diffraction intensities are small, it is important to know where in reciprocal space these effects are expected to occur and to what extent experiment can settle theoretical disputes. In the present work the deformation density in the water molecule was calculated using the Hartree-Fock and the Density Functional method, with various basis sets. Each of the resulting distributions was Fourier transformed and temperature factors corresponding to 100 K and 300 K were applied. In particular, the imaginary component of the structure factors contains much information. With respect to the dimer, a hypothetical centrosymmetric crystal was constructed and the Fourier components of the electron density distribution calculated. Fourier summations of shells in reciprocal space were made to identify the regions in reciprocal space that contain the information required.

The chemical bond and the entropy of electrondensity distribution in molecules

The chemical bond and the entropy of electrondensity distribution in molecules

Chemical bond and entropy of the electron density distribution in molecules

Chemical bond and entropy of the electron density distribution in molecules

The chemical bond and the entropy of the electron density distribution in molecules I. H 2 + and H2

The chemical bond and the entropy of the electron density distribution in molecules I. H 2 + and H2

Tangent-sphere models of molecules. I. Theory and construction

This discussion of the electronic structure of molecules is based upon the direct use of the total electron density distribution in molecules and upon two fundamental principles that presumably govern the nature of this distribution: the Pauli principle and the Hellmann-Feynman theorem.