Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It includes the general shape of the molecule as well as bond lengths, bond angles, torsional angles and any other geometrical parameters that determine the position of each atom.
A hypervalent molecule (the phenomenon is sometimes colloquially known as expanded octet) is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Phosphorus pentachloride (PCl5), sulfur hexafluoride (SF6), chlorine trifluoride (ClF3), the chlorite (ClO2−) ion, and the triiodide (I3−) ion are examples of hypervalent molecules.
Valence shell electron pair repulsion theory, or VSEPR theory, is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gillespie-Nyholm theory after its two main developers, Ronald Gillespie and Ronald Nyholm. The premise of VSEPR is that the valence electron pairs surrounding an atom tend to repel each other and will, therefore, adopt an arrangement that minimizes this repulsion. This in turn decreases the molecule's energy and increases its stability, which determines the molecular geometry. Gillespie has emphasized that the electron-electron repulsion due to the Pauli exclusion principle is more important in determining molecular geometry than the electrostatic repulsion.
Apicophilicity is the phenomenon in which electronegative substituents of trigonal bipyramidal pentacoordinate compounds prefer to occupy apical positions (Lap).
In chemistry, orbital hybridisation is the concept of mixing atomic orbitals into new hybrid orbitals suitable for the pairing of electrons to form chemical bonds in valence bond theory. Hybrid orbitals are very useful in the explanation of molecular geometry and atomic bonding properties and are symmetrically disposed in space. Although sometimes taught together with the valence shell electron-pair repulsion (VSEPR) theory, valence bond and hybridisation are in fact not related to the VSEPR model.
In chemistry, a trigonal pyramid is a molecular geometry with one atom at the apex and three atoms at the corners of a trigonal base, resembling a tetrahedron (not to be confused with the tetrahedral geometry). When all three atoms at the corners are identical, the molecule belongs to point group C3v. Some molecules and ions with trigonal pyramidal geometry are the pnictogen hydrides (XH3), xenon trioxide (XeO3), the chlorate ion, ClO−
3, and the sulfite ion, SO2−
3. In organic chemistry, molecules which have a trigonal pyramidal geometry are sometimes described as sp3 hybridized. The AXE method for VSEPR theory states that the classification is AX3E1.
There are three series of binary phosphorus halides, containing phosphorus in the oxidation states +5, +3 and +2. All compounds have been described, in varying degrees of detail, although serious doubts have been cast on the existence of PI5. Mixed chalcogen halides also exist.
In chemistry, octahedral molecular geometry describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N-H bonds, is referred to as octahedral.
In chemistry, Bent's rule describes and explains the relationship between the orbital hybridization of central atoms in molecules and the electronegativities of substituents. The rule was stated by Henry A. Bent as follows:
Atomic s character concentrates in orbitals directed toward electropositive substituents.
Sulfur tetrafluoride is the chemical compound with the formula SF4. It is a colorless gas. It is a corrosive species that releases dangerous HF upon exposure to water or moisture. Despite these unwelcome characteristics, this compound is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.
The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerize by exchanging the two axial ligands (see Figure at right) for two of the equatorial ones. It is the most widely accepted mechanism for pseudorotation and most commonly occurs in trigonal bipyramidal molecules such as PF5, though it can also occur in molecules with a square pyramidal geometry. The Berry mechanism is named after R. Stephen Berry, who first described this mechanism in 1960.
Fluxional molecules are molecules that undergo dynamics such that some or all of their atoms interchange between symmetry-equivalent positions. Because virtually all molecules are fluxional in some respects, e.g. bond rotations in most organic compounds, the term fluxional depends on the context and the method used to assess the dynamics. Often, a molecule is considered fluxional if its spectroscopic signature exhibits line-broadening due to chemical exchange. In some cases, where the rates are slow, fluxionality is not detected spectroscopically, but by isotopic labeling. Where such movement does not occur, the molecule may be described as a semi-rigid molecule. Longuet-Higgins introduced the use of permutation-inversion groups for the symmetry classification of the states of fluxional molecules.
Phosphorus pentafluoride, PF5, is a phosphorus halide. It is a colourless, toxic gas that fumes in air.
In molecular geometry, square pyramidal geometry describes the shape of certain compounds with the formula ML5 where L is a ligand. If the ligand atoms were connected, the resulting shape would be that of a pyramid with a square base. The point group symmetry involved is of type C4v. The geometry is common for certain main group compounds that have a stereochemically active lone pair, as described by VSEPR theory. Certain compounds crystallize in both the trigonal bipyramidal and the square pyramidal structures, notably [Ni(CN)5]3−.
Disphenoidal or Seesaw is a type of molecular geometry where there are four bonds to a central atom with overall C2v molecular symmetry. The name "seesaw" comes from the observation that it looks like a playground seesaw. Most commonly, four bonds to a central atom result in tetrahedral or, less commonly, square planar geometry.
In chemistry, the linear molecular geometry describes the geometry around a central atom bonded to two other atoms placed at a bond-angle of 180°. Linear organic molecules, such as acetylene (HC≡CH), are often described by invoking sp orbital hybridization for their carbon centers.
In chemistry, molecules with a non-collinear arrangement of two adjacent bonds have bent molecular geometry. Certain atoms, such as oxygen, will almost always set their two (or more) covalent bonds in non-collinear directions due to their electron configuration. Water (H2O) is an example of a bent molecule, as well as its analogues. The bond angle between the two hydrogen atoms is approximately 104.45°. Nonlinear geometry is commonly observed for other triatomic molecules and ions containing only main group elements, prominent examples being nitrogen dioxide (NO2), sulfur dichloride (SCl2), and methylene (CH2).
In chemistry, T-shaped molecular geometry describes the structures of some molecules where a central atom has three ligands. Ordinarily, three-coordinated compounds adopt trigonal planar or pyramidal geometries. Examples of T-shaped molecules are the halogen trifluorides, such as ClF3.
In chemistry, the pentagonal planar molecular geometry describes the shape of compounds where five atoms, groups of atoms, or ligands are arranged around a central atom, defining the vertices of a pentagon.
In chemistry, the capped octahedral molecular geometry describes the shape of compounds where seven atoms or groups of atoms or ligands are arranged around a central atom defining the vertices of a gyroelongated triangular pyramid. This shape has C3v symmetry and is one of the three common shapes for heptacoordinate transition metal complexes, along with the pentagonal bipyramid and the capped trigonal prism.
