Triple-bond covalent radii

A system of additive covalent radii is proposed for sigma(2) pi(4) triple bonds involving elements from Be to E 112 (eka-mercury). Borderline cases with weak multiple bonding are included. Only the elements in Group 1, the elements Zn-Hg in Group 12 and Ne in Group 18 are then totally excluded. Gaps are left at late actinides and some lanthanides. The standard deviation for the 324 included data points is 3.2 pm.     

Experimental determination of covalent radii of elements

The results of direct experimental determination of covalent bond lengths in molecular structures are presented. This made it possible to establish the values of normal covalent radii. The recommended values of covalent radii for 56 elements are tabulated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2349–2354, December, 1995.     

Electrostatic and covalent interactions in CdTe nanocrystalline assemblies

This paper focuses on the interactions between cysteamine-stabilized CdTe nanocrystals [CdTe(CA) NCs] and thioglycolic-acid-stabilized CdTe nanocrystals [CdTe(TGA) NCs]. These interactions were examined by the absorption, continuous, and time-resolved photoluminescence (PL) spectra of the electrostatically mixed and the covalently linked NCs assemblies comprised of the oppositely surface charged CdTe(CA) and CdTe(TGA) NCs and by a comparison with those of the corresponding pristine NCs. The CdTe(CA)-CdTe(TGA) coupling is dictated by the surfactant spacer, ranging between 0.93 and 1.14 nm and by electrostatic and covalent interactions, enabling a F?rster resonance energy transfer (FRET) process among the NCs. The results revealed an excellent spectral overlap between the emission of the CdTe(TGA) NCs and the absorption of the CdTe(CA) NCs as well as a PL spectral red shift on the formation of electrostatic and covalent interactions. Furthermore, the measurements showed a lifetime ranging between 1.2 and 3 ns for the electrostatically mixed and the covalently linked assemblies, shorter than those of the pristine CdTe(CA) NCs and CdTe(TGA) NCs, both of which measured as approximately 5.5 ns. When CdTe(TGA) NCs performed as the most efficient donors, FRET rates of 10(10)-10(11) s(-1) were calculated for the electrostatically mixed NCs or covalently linked NCs.     

Electrostatic molecular potentials: Mulliken approximation

The electrostatic potential is calculated, in the LCAO framework, through Mulliken's approximation. An extremely simplified form of the potential expression is obtained, with a degree of accuracy comparable to a full ab initio treatment. Other related possible simplifications are also discussed.     

Electrostatic molecular potentials in hydrogen-bonded systems

A study is made of the modifications of the electrostatic molecular potential brought about by hydrogen bonding both in the hydrogen-bond region itself and in the external regions of the proton-acceptor and proton-donor molecules. Systems up to four successive units in a chain of donor-acceptors are considered. The possibility of obtaining a satisfactory picture of the global potential by a simple superposition of the potentials of the individual units is evaluated.     

Electrostatic potentials in periodic boundary conditions

We discuss the effects of using periodic boundary conditions on the statistical mechanics of particles with electrostatic interactions. For the system of particles with electrostatic interactions plus periodic boundary conditions we develop an effective interaction which may be used with ordinary boundary conditions. The lattice sums which arise from the periodic boundary conditions contain divergences. We use a variant of Ewald's method to evaluate the sums which makes the handling of the divergences fairly simple. We discuss the effect of the effective interaction on the thermodynamics of the system.     

Electrostatic potentials of strained systems: nitrocyclopropane

The presence of an NO₂ substituent is found to eliminate the negative electrostatic potentials associated with the “bent” CC bonds cyclopropane. This is presumably due in large part to a rearrangement of electronics charge caused by the nitro group, as is shown by electronic density difference plots. Bond path calculations reveal bent bonds in nitrocyclopropane that are very similar to those in cycloprophane.     

Electrostatic and covalent contributions in the coordination bonds of transition metal complexes

To develop a molecular mechanics force field for modeling complexes of transition metals and organic ligands, the electrostatic and covalent contributions in the coordination bonds were investigated using quantum mechanical density functional theory and model complexes of glyoxal diimine and the 2+ cations of the first row transition metals. The VDD and Hirshfeld charges are found to be closely correlated with the extent of the electron transfer between the ligands and the cations. Assuming the electrostatic contribution can be represented by the atomic partial charges, the covalent contributions in the coordination bonds are estimated to be in a range of 54-92% for the systems calculated. A simple force field was parametrized to validate the partial charge representation.     

Electrostatic potentials and fields in the vicinity of engineered nanostructures

We have developed a method for calculating the electrostatic potentials and fields in the vicinity of geometrically complex engineered nanostructures composed of varying materials in electrolytes of arbitrary pH and ionic strength. The method involves direct summation of charged Debye-Hückel spheres composing the nanostructural surfaces and, by including charge redistribution on the surface of conducting materials held at constant potential, is applicable to mixed boundary conditions. The method is validated by comparison to analytical solutions for an infinite plane (Gouy-Chapman), an infinite cylinder (Bessel functions), and an infinite plane which contains a hole and which is held at constant potential. Excellent agreement between the potentials obtained by our numerical method and the closed form solutions is found for these conditions. The method is applied to the calculation of the electric field enhancement in the vicinity of a nanomembrane whose pore wall is held at constant charge and whose membrane surfaces are held at constant potential. The electric field is found to be enhanced by the charge buildup in the rim of the hole of the nanomembrane; the buildup results from the potential being held constant in the conducting region. Ion concentrations are also calculated. Positive ion rejection is found to be enhanced by this charge buildup in the region of the rim when a constant positive potential is applied.     

Gaussian multipoles in practice: Electrostatic energies for intermolecular potentials

A method is presented for calculating the total electrostatic interaction energies between molecules from ab initio monomer wave functions. This approach differs from existing methods, such as Stone's distributed multipole analysis (DMA), in including the short-range penetration energy as well as the long-range multipolar energy. The monomer charge densities are expressed as distributed series of atom-centered functions which we call Gaussian multipoles; these are analogous to the distributed point multipoles used in DMA. Our procedure has been encoded in the GMUL program. Calculations have been performed on the formamide/formaldehyde complex, a model system for N? H …? O hydrogen bonding in biological molecules, and also on guanidinium/benzene, modeling amino/aromatic interactions in proteins. We find that the penetration energy can be significant, especially in its contribution to the variation of the electrostatic energy with interaction geometry. A hybrid method, which uses Gaussian multipoles for short-range atom pair interactions and point multipoles for long-range ones, allows the electrostatic energies, including penetration, to be calculated at a much reduced cost. We also note that the penetration energy may provide the best route to an atom–atom anisotropic model for the exchange-repulsion energy in intermolecular potentials. © 1994 by John Wiley & Sons, Inc.     

Electrostatic potentials and fields from density expansions of deformed atoms in molecules

The exact representation of the molecular density by means of atomic expansions, consisting in spherical harmonics times analytical radial factors, is employed for the calculation of electrostatic potentials, fields, and forces. The resulting procedure is equivalent to an atomic multipolar expansion in the long-range regions, but works with similar efficiency and accuracy in the short-range region, where multipolar expansions are not valid. The performances of this procedure are tested on the calculation of the electrostatic potential contour maps and electrostatic field flux lines of water and nitrobenzene, computed from high-quality molecular electron densities obtained with Slater basis sets.     

A nearly complete system of average crystallographic ionic radii and its use for determining ionization potentials

Available systems of empirical (crystallographic) ionic radii are compared. All these systems turn out to be compatible if the O^2? radius is taken to be 0.140 nm. The choice of the oxygen ionic radius is dictated by the equality of the metal ion-oxygen ion distances in oxide crystals and the metal ion-oxygen atom distances in crystal hydrates and concentrated aqueous solutions. In all systems of empirical ionic radii under consideration, the uncertainty of determination of ionic radii is 0.002–0.005 nm. A new method of determination of the ionic radii of elements in unusual valence states is suggested: from the empirical dependence of the electron density at an atom in a given valence state on the atomic radius, a two-parameter equation relating the ionic radii of Period 4–7 elements in two valence states is derived, which allows one to calculate the ionic radius that cannot be determined by crystallography because of the lack of stable compounds in this valence state. Ionic radii are calculated for all Period 4–7 elements in all valence states. They constitute a nearly complete system of ionic radii. There is a linear relationship between the atomic nucleus charge and the inverse ionic radius. It is shown that the square root of the ionization potential is a linear function of the inverse ionic radius. The as yet experimentally unknown ionization potentials of 78 ions of different elements are estimated.     

Electrostatic potentials of some dibenzo-p-dioxins in relation to their biological activities

A computational analysis of the electrostatic potentials of eight halogenated dibenzo-p-dioxins has been carried out at theab initio SCF STO-5G level. It focuses upon the relationships between these potentials and the biological activities of the molecules, including toxicity, aryl hydrocarbon hydroxylase induction and receptor binding. In general, regions of negative potential are found to be associated with the oxygens and with the halogen substituents. Biological activity appears to be related to the presence of an optimum range of negative potentials above the lateral portions of the molecules in conjunction with a weakening of those near the oxygens.     

Electrostatic potentials,fields and field gradients from a general crystalline charge density

Explicit expressions for the electrostatic potential, the electric field and the electric field gradient at the nuclear positions of a crystalline lattice are presented. They are derived for a charge density given as an expansion in terms of spherical harmonics around the nuclear sites and as a Fourier series in the interstitial. These expressions can be decomposed into contributions from the spherical region centered around the lattice site of interest, from spherical regions surrounding all the other lattice sites and a contribution from the interstitital region.     

Electrostatic potentials in systems periodic in one, two, and three dimensions

We consider the electrostatic potential in a unit cell containing N point charges Q(j) with positions r(j) inside the cell. The cell is replicated periodically in one, two, and three dimensions. The purpose is to give representations for the potential which contain only lattice sums which are absolutely convergent and uniformly convergent in the sampling position r. These representations are derived using variants of the Ewald method and are primarily intended for use in evaluating the accuracy of any algorithm to evaluate electrostatic energies and forces in simulations of dense matter, rather than necessarily for use of themselves in simulations. In reduced dimensionality the Ewald representations can be numerically inefficient and other representations are also provided with careful specification which allows two forms to be used for the potential functions in order to improve numerical performance. These mixed representations may be satisfactory in simulations.     

Atomic number dependences of atomic radii and ionization potentials according to “Multicomponent Electron Gas” theory

Multicomponent electron gas theory is applied to describe the chemically significant properties of atoms, such as atomic radii and ionization potentials. The dependence of these characteristics on the atomic number is described.     

Electrostatic and Non‐covalent Interactions in Dicationic Imidazolium–Sulfonium Salts with Mixed Anions

A series of thioether‐functionalised imidazolium salts have been prepared and characterized. Subsequent reaction of the thioether‐functionalised imidazolium salts with iodomethane affords imidazolium–sulfonium salts composed of doubly charged cations and two different anions. Imidazolium–sulfonium salts containing a single anion type are obtained either by a solvent extraction method or by anion exchange. The imidazolium–sulfonium salts undergo a methyl‐transfer reaction on exposure to water, giving rise to a new, singly charged imidazolium salt with iodide introduced at the 2‐position of the imidazolium ring. Crystal structures of some of the imidazolium–sulfonium salts were determined by X‐ray crystallography providing the topology of the interactions between the dications and the anions. Electrospray ionization mass spectrometry and quantum‐chemical calculations were used to rationalise the relative strength of these interactions.     

Covalent radii revisited

A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96. The proposed radii show a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking, notably the noble gases. The proposed set of radii therefore fills most of the gaps and solves some inconsistencies in currently used covalent radii. The transition metal and lanthanide contractions as well as the differences in covalent atomic radii between low spin and high spin configurations in transition metals are illustrated by the proposed radii set.