What areelectrons really doing in molecules, discovered Mulliken

What are the electrons really doing in molecules, discovered Mulliken

7:01 AM, 7th June 2012
What are the electrons really doing in molecules, discovered Mulliken
Robert S Mulliken, the person primarily responsible for the early development of molecular orbital theory.

SINGAPORE: Robert Sanderson Mulliken born on 7 June 1896 was a physicist and chemist. He is primarily responsible for the early development of molecular orbital theory, the elaboration of the molecular orbital method of computing the structure of molecules. Dr Mulliken received the Nobel Prize for chemistry in 1966 for his work on ‘fundamental work concerning chemical bonds and the electronic structure of molecules.’ He received the Priestley Medal in 1983 (highest honour conferred by the American Chemical Society).

Mulliken has made many contributions to chemistry, the most important one being the molecular orbital theory, a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule. The theory was developed by Mulliken and Friedrich Hund and hence also known as Hund-Mulliken theory.

His other contributions to chemistry are the discovery of bands due to diatomic carbon, C2, that proposed the controversial concept of hyperconjugation to explain the shortening on carbon-carbon bonds adjacent to unsaturated carbon atoms. This work led to the elucidation of the structure of diborane, B2H6. Mulliken also worked toward the development of semi-empirical methods for calculating electronic energies, including the all electron self-consistent field method (SCF), which provided the foundation for all subsequent abinitio calculations.

Mulliken also proposed the concept of a charge transfer complex while studying the complex formed between iodine and benzene, a definition of electronegativity as ½(I+E), and the concept of the overlap integral as a measure of bond strength. He predicted chemical and physical properties of molecules in linear combination of atomic orbitals- molecular orbitals- SCF (LCAO-MO-SCF) orbital and won wide approval and application. Today, this provides the foundation of the frontier orbital method so widely used in organic chemistry.

Apart from Nobel Prize and Priestley Medal, Mulliken received many awards and honours. He was awarded the GN Lewis Gold Medal, Debye award, Richards Medal and Gibbs Medal. Mulliken was awarded honourary degrees from the Universities of Columbia, Stockholm, Marquette, Cambridg, and Gustavus Adolphus College.

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