Molecular Geometry - Bonding

Bonding

Molecules, by definition, are most often held together with covalent bonds involving single, double, and/or triple bonds, where a "bond" is a shared pair of electrons (the other method of bonding between atoms is called ionic bonding and involves a positive cation and a negative anion).

Molecular geometries can be specified in terms of bond lengths, bond angles and torsional angles. The bond length is defined to be the average distance between the centers of two atoms bonded together in any given molecule. A bond angle is the angle formed between three atoms across at least two bonds. For four atoms bonded together in a chain, the torsional angle is the angle between the plane formed by the first three atoms and the plane formed by the last three atoms.

There exists a mathematical relationship among the bond angles for one central atom and four peripheral atoms (labeled 1 through 4) expressed by the following determinant. This constraint removes one degree of freedom from the choices of (originally) six free bond angles to leave only five choices of bond angles. (Note that the angles, and are always zero.)

0 = \begin{vmatrix} \cos \theta_{11} & \cos \theta_{12} & \cos \theta_{13} & \cos \theta_{14} \\ \cos \theta_{21} & \cos \theta_{22} & \cos \theta_{23} & \cos \theta_{24} \\ \cos \theta_{31} & \cos \theta_{32} & \cos \theta_{33} & \cos \theta_{34} \\ \cos \theta_{41} & \cos \theta_{42} & \cos \theta_{43} & \cos \theta_{44} \end{vmatrix}

Molecular geometry is determined by the quantum mechanical behavior of the electrons. Using the valence bond approximation this can be understood by the type of bonds between the atoms that make up the molecule. When atoms interact to form a chemical bond, the atomic orbitals are said to mix in a process called orbital hybridisation. The two most common types of bonds are sigma bonds and pi bonds. The geometry can also be understood by molecular orbital theory where the electrons are delocalised.

An understanding of the wavelike behavior of electrons in atoms and molecules is the subject of quantum chemistry.

Read more about this topic:  Molecular Geometry

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