Born repulsion between ions in the gas phase is explained by overlapping electron clouds
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While literature discusses short-range repulsion and Born-Mayer potentials, the provided sources do not sufficiently establish that Born repulsion specifically in the gas phase is solely explained by overlapping electron clouds.
Short-range repulsion within intermolecular force fields is conventionally described by either Lennard-Jones (A/r(12)) or Born-Mayer (A exp(-Br)) forms. Despite their widespread use, these simple functional forms are often unable to describe the interaction energy accurately over a broad range of intermolecular distances, thus creating challenges in the development of ab initio force fields and potentially leading to decreased accuracy and transferability. Herein, we derive a novel short-range functional form based on a simple Slater-like model of overlapping atomic densities and an iterated stockholder atom (ISA) partitioning of the molecular electron density. We demonstrate that this Slater-ISA methodology yields a more accurate, transferable, and robust description of the short-range interactions at minimal additional computational cost compared to standard Lennard-Jones or Born-Mayer approaches. Finally, we show how this methodology can be adapted to yield the standard Born-Mayer functional form while still retaining many of the advantages of the Slater-ISA approach.
When the Mg2+ ion is replaced by two acetylcholine ions the quaternary heads of the latter are positioned so that they form two mutually repelling ACh+ receptor group dipoles. As the Mg2+ ion leaves, its rehydration energy contributes to the sum of the electron cloud repulsions and the ACh+ receptor group dipole repulsions, causing the receptor groups to be forced apart activating the receptor macromolecule. The subsequent decrease in ACh+ concentration results in the reestablishment of the resting state. The coulombic electrostatic energy, the Born repulsion energy, the London attraction energy and the oxyanion ACh+ dipole repulsion energies have been calculated and shown to be consistent with the model. The displacement of the Mg2+ by two ACh+ ions makes several hundred kcals of energy available for receptor group separation and receptor activation. Published in Journal of theoretical biology (1985)
Abstract The deviations from the equation of state for perfect gases which are observed in all known gases result from the interactions of their constituent atoms or molecules. The excess pressures observed at all but the lowest temperatures show that the dominating factor is the strong repulsion between atoms at close renge, due to the interpentration of complete electron shells. Little is known about these repulsions, and that is readily summarized. Between atoms with spherically symmetrical distributions it is likely that the repulsive potential is accurately represented by a function P(r)e-r/p, (1) Where r is separation of the atomic nuclei and P(r) a polynomial in r. Quantum theoretical calculations made by Slater (1928) for helium atoms (with a closed shell of two electrons) and by Bleick and Mayer (1934) for neon atoms (with a closed shell of eight electrons) show that an adequate expression may sometimes be obtained if the polynomial is replaced by a constant. Some confirmation of this (though over a very restricted range of r) is given by Born and Mayer (1932) and Huggins (1937), whose work on ionic cubic crystals shows that their elastic properties are admirably correlated when the repulsive potential of two ions of rare gas type is represented by an exponential function be-r/p, with a range of about one atomic diameter.
from the nucleus begins to outweigh the repulsion between electrons that causes electron clouds to expand: thus for example ionic radii decrease in the series
The periodic table, also known as the periodic table of the elements, is an ordered arrangement of the chemical elements into rows ("periods") and columns ("groups"). An icon of chemistry, the periodic table is widely used in physics and other sciences. It is a depiction of the periodic law, which states that when the elements are arranged in order of their atomic numbers an approximate recurrence
The following table shows the electron configuration of a neutral gas-phase atom of each element. Different configurations can be favoured in different chemical environments. The main-group elements have entirely regular electron configurations; the…
Thallium and lead atoms are about the same size as indium and tin atoms respectively, but from bismuth to radon the 6p atoms are larger than the analogous 5p atoms. This happens because when atomic nuclei become highly charged, special relativity becomes needed to gauge the effect of the nucleus on the electron cloud. These relativistic effects result in heavy elements increasingly having differing properties compared to their lighter homologues in the periodic table. Spin–orbit interaction splits the p subshell: one p orbital is relativistically stabilized and shrunken (it fills in thallium and lead), but the other two (filling in bismuth through radon) are relativistically destabilized and expanded. Relativistic effects also explain why gold is golden and mercury is a liquid at room temperature. They are expected to become very strong in the late seventh period, potentially leading to a collapse of periodicity. Electron configurations are only clearly known until element 108 (hassium), and experimental chemistry beyond 108 has only been done for elements 112 (copernicium) through 115 (moscovium), so the chemical characterization of the heaviest elements remains a topic of current research.
The trend that atomic radii decrease from left to right is also present in ionic radii, though it is more difficult to examine because the most common ions of consecutive elements normally differ in charge. Ions with the same electron configuration decrease in size as their atomic number rises, due to increased attraction from the more positively charged nucleus: thus for example ionic radii decrease in the series Se2−, Br−, Rb+, Sr2+, Y3+, Zr4+, Nb5+, Mo6+, Tc7+. Ions of the same element get smaller as more electrons are removed, because the attraction from the nucleus begins to outweigh the repulsion between electrons that causes electron clouds to expand: thus for example ionic radii decrease in the series V2+, V3+, V4+, V5+.
Evidence is presented that there is a clear covalent component in the bonding of Au+ to Kr and Au+ to Xe, with some evidence that there may be such bonding between Au+ and Ar; for Au+ and Ne, there is no such evidence, and the bonding seems to be entirely physical. A model potential analysis shows that when all attractive inductive and dispersive terms out to R-8 are properly included in the Au+-Ne case, with an Ae(-bR) Born-Mayer repulsive term, essentially all the bonding in Au+-Ne can be rationalized by physical attraction alone. This is consistent with a natural bond order (NBO) analysis of the Au+-Ne ab initio wavefunctions, which shows the charge on Au+ to be very close to 1.0. In contrast, similar model potential and NBO analyses show quite clearly that physical interactions alone cannot account for the large bond energy values for the Au+-Kr and Au+-Xe complexes and are consistent with covalent contributions to the Au+-Kr and Au+-Xe interactions. Au+-Ar is seen to lie on the borderline between these two limits. In performing the model potential analyses, high-level ab initio calculations are employed [CCSD(T) energies, extrapolated to the complete basis set limit], to obtain reliable values of Re, De and omegae as input. A comparison of the gold-Xe bond distances in several solid-state Au(I, II and III) oxidation-state complex ions, containing "ligand" Xe atoms, prepared by Seppelt and co-workers, with that of the "free" Au+-Xe gas-phase ion is made, and a discussion of the trends is presented.
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