BONDING VERSUS INTERACTION: Intra- and intermolecular forces When considering BONDing types (intramolecular), it is instructive to examine and

reference the extreme types. I will use three fundamental extreme types: (1) Metallic (2) Covalent (3) Ionic INTERACTIONS between molecules (atoms) are often much weaker and do not involve significant orbital overlapping. From strongest to weakest: (1) Hydrogen bonding (H with FON) (2) Dipole-dipole forces (3) London-dispersion or VDW forces (instantaneous dipoles) The first two intermolecular forces are often associated with POLAR molecules. VDW forces are very weak and constant background forces that become significant in the interaction between NONPOLAR molecules. Rigorous definitions or distinctions between the bonding types can be deduced from the degree of overlapping of the wavefunctions. The above categories are qualitative. Covalent bonds: electron density or WF overlap amplitude is greatest between nuclei. Ionic bonds: WF amplitude or electron density (transfers completely to one atom and thus) is greatest around (alternating) nuclei. Metallic bonding: electron density is delocalized everywhere so energy splitting leads not to discrete levels but broad energy bands. Covalent bonding, valence electrons between atoms are shared in localized clouds. Ionic bonding, valence electrons transfer to the less EN element and the positive and negative elements held together by electrostatic attraction. Pure ionic bonding cannot exist and ALL ionic bonds have some covalent character (i.e. some sharing of electrons). Ionic bonds are held together mostly by electrostatic attraction between oppositely charged elements, while covalently bonded atoms are bound by sharing electrons to attain stable EC. GEOMETRY: covalent = VSPER (steric number or domains); ionic = maximum packing rules (arranging a bunch of differently sized balls in the smallest possible box or space). If we however imagine pure ionic bonding as pure attraction between positive and negative charges, then the attraction felt between ions is governed by Coulombs law where the force of attraction is proportional to the product of the charges over the square distance. Theoretically we can imagine the total energy of this bond as the sum of the energy required to remove an electron from one atom, and the energy gained from adding an electron to the other atom:

IE(Na) = +5.14eV EA(Cl)= 3.71eV => requires expenditure of 1.43eV to transfer one e- from Na to Cl. However, E lowering from electrostatic attraction is about 4.51eV which lowers the E of the system by a total of 3.08eV.

Si O bond is considered 50% ionic and 50% covalent. Two fundamental or extreme type of bonds: electrons shared or pure electrostatic attraction. There are no chemical bonds between molecules, atoms (metals), or ions; they are held together by intermolecular Coulombic forces. Solids often imply crystalline as opposed to amorphous. Crystalline solids involve three types: 1) molecular (held by intermolecular forces, weak), 2) atomic (metallic or network covalent), 3) ionic (positive and negative ions attracting) Chemical bonds require large energy to overcome, 100-1000kJ/mole of bonds (as opposed to intermolecular).

Hydrogen bonds are on order of 0.1eV/bond. VDW ~0.1eV/bond, and varies as r-6 (thus the strength of the bond extinguishes extremely rapidly with distance).