VSEPR-Valence shell electron pair repulsion

Valence shell electron pair repulsion (VSEPR) rules are a model in chemistry used to predict the shape of individual molecules based upon the extent of electron-pair electrostatic repulsion.[1] It is also named GillespieNyholm theory after its two main developers. The acronym "VSEPR" is sometimes pronounced "vesper" for ease of pronunciation; however, the phonetic pronunciation is technically more correct. The premise of VSEPR is that the valence electron pairs surrounding an atom mutually repel each other, and will therefore adopt an arrangement that minimizes this repulsion, thus determining the molecular geometry. The number of atoms bonded to a central atom plus the number of lone pairs of its nonbonding valence electrons is called its steric number. VSEPR theory is usually compared and contrasted with valence bond theory, which addresses molecular shape through orbitals that are energetically accessible for bonding. Valence bond theory concerns itself with the formation of sigma and pi bonds. Molecular orbital theory is another model for understanding how atoms and electrons are assembled into molecules and polyatomic ions. VSEPR theory has long been criticized for not being quantitative, and therefore limited to the generation of "crude", even though structurally accurate, molecular geometries of covalent molecules. However, molecular mechanics force fields based on VSEPR have also been developed.

Valence Shell Electron Pair Repulsion Theory

Valence shell electron pair repulsion theory, VSEPR, is a super-simple technique for predicting the shape or geometry of atomic center in small molecules and molecular ions:

Crucially, atomic center with VSEPR determined geometry can be joined together into molecular entities like cyclohexane and glucose:

This molecular building-block logic can be extended, enabling large bio molecular structures like DNA to be modelled and understood:

The VSEPR Technique

Six or so steps are required to generate the VSEPR geometry of an atomic centre such as: Carbon in methane, CH4 Nitrogen in ammonia, NH3 Xenon in xenon tetra fluoride, XeF4 Iodine in the iodide di fluoride ion, [IF2] First, determine the number of electrons in the outer (valence) shell about the central atom (C, N, Xe, I, etc.):

Carbon, for example has four valence electrons, nitrogen 5, etc. Second, find valency and number of electrons associated with the ligand X:

Third, construct a valid Lewis structure of the molecule in question showing all of the bonds and all of the lone pairs (nonbonded pairs) of electrons. If the structure is a molecular ion, add one valence electron for each negative charge and remove one valence electron for each positive charge.

Not all Lewis structures have eight electrons about the central atom A (as emphasized by very simple Lewis octet theory). For example, Sulfuric acid, H2SO4, has two monovalent OH functions and two doubly bonded oxygen that behave as single ligands:

Phosphorus pentachloride, PCl5, has 10 electron

Valence-Shell Electron-Pair Repulsion (VSEPR) Models

The 3-dimensional structure of BF3 is different from PF3, and this is difficult to comprehend by considering their formulas alone. However, the Lewis dot structure for them are different, and the electron pair in :PF3 is the reason for its structure being different from BF3 (no lone pair). Three-dimensional arrangements of atoms or bonds in molecules are important properties as are bond lengths, bond angles and bond energies. The Lewis dot symbols led us to see the nonbonding electron pairs, whose role in determining the shape of a molecule was examined by N.V. Sidgwick and H.E. Powell in 1940, and later by R.S. Nyholm and R.J. Gillespie. They have developed an extensive rationale called valence-shell electron-pair repulsion (VSEPR) model of molecular geometry. The Valence-Shell Electron-Pair Repulsion (VSEPR) models consider the unshared pairs (or lone electron pairs) and the bonding electrons. This considerations of lone and bonding electron pairs give an excellent explanation about the molecular shapes. The VSEPR model counts both bonding and nonbonding (lone) electron pairs, and call the total number of pairs the steric number (SN). If the element A has m atoms bonded to it and n nonbonding pairs, then SN = m + n SN is useful for predicting shapes of molecules. If X is any atom bonded to A (in single, double, or triple bond), a molecule may be represented by AXmEn where E denote a lone electron pair. This formula enable us to predict its geometry. The common SN, descriptor, and examples are given in the table on the right. Molecular shapes and steric numbers (SN) Example SN Descriptor BeCl2, CO2 2 Linear BF3, SO3 Trigonal planar 3 SO2E, OO2E bent CH4 Tetrahedral NH3E 4 pyramidal H2OE2 bent PF5 Trigonal bypyramidal SF4E 5 butterfly ClF3E2 T-shape SF6, OIF5 octahedral BrF5E 6 pyramidal XeF4E2 square planar E represents a lone electron pair. SN is also called the number of VSEPR pairs or number of electron pairs.

Note that the SN is also called the number of VSEPR pairs or number of electron pairs. The VSEPR model has another general rule: lone pairs of electrons take up more space than bonded pairs making the bond angle, say H-O-H for water less than the tetrahedral angle of 109.5 . Actually, the H-O-H angle in water is 105 . The geometry of the molecules with their SNs equal to 2 to 6 are given in the Table. The first line for each is the shape including the lone electron pair(s). If the lone electron pairs are ignored, the geometry of the molecule is given by another descriptor.

The VSEPR theory assumes that each atom in a molecule will achieve a geometry that minimizes the repulsion between electrons in the valence shell of that atom. The five compounds shown in the figure below can be used to demonstrate how the VSEPR theory can be applied to simple molecules.