Chemical bonds and population analysis

10 Chemical bonds and population analysis Most metals of interest in the context of polymer-based electronic devices form some kind of chemical bond to the polymer upon interaction with a polymer surface. Population analysis, based on the electronic structure, is used to determine the character of this bond. According to the commonly used chemical terminology, bonds are classified as ionic if the bonded atoms are oppositely charged and held together by the attractive Coulomb force, and covalent if the two atoms are neutral but share the same pair of electrons. In the latter case, much of the electron density is located between the bonded atoms whereas for the ionic bond the charge density is concentrated at the atomic sites. 

The degree of ionicity in the bond between a metal atom and a polymer, or molecule, is related to the ionization potential and electron affinities of the substituents. The metals we have studied are of interest as electron injecting contacts in electronic devices. These metals must have a low ionization potential (or work function), of the same order as the electron affinity of the polymer, in order for the charge transfer process to occur. If the ionization potential of the metal is lower than the polymery-electron affinity, spontaneous charge transfer occurs which is the signature of an ionic bond. Thus, the character of the charge distribution in the metal-polymer complexes we are studying is related to the situation in the electronic device. 

The summation over i includes all occupied levels of the energy eigenvalue spectrum. In the case of a closed shell system this number equals N/2, where Nis the number of electrons in the system. Using eqs. (2.8) and (2.35), the electronic charge density can be expressed as  

Using the definition of the overlap matrix (see eq. (2.11) above) we can rewrite this as  

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