What is the Hund-Mulliken molecular orbital theory?

1 Answer
Apr 23, 2018


It was the precursor (in name) of the modern Molecular Orbital (MO) theory.


In chemistry, molecular orbital theory (MO theory) is 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.

In this theory, each molecule has a set of molecular orbitals, in which it is assumed that the molecular orbital wave function ψf may be written as a simple weighted sum of the n constituent atomic orbitals χi.


Molecular orbital theory was developed, in the years after valence bond theory (1927) had been established, primarily through the efforts of Friedrich Hund, Robert Mulliken, John C. Slater, and John Lennard-Jones.[3] MO theory was originally called the Hund-Mulliken theory.[4]

The word orbital was introduced by Mulliken in 1932.[4] By 1933, the molecular orbital theory had become accepted as a valid and useful theory.[5] According to German physicist and physical chemist Erich Hückel, the first quantitative use of molecular orbital theory was the 1929 paper of Lennard-Jones.[6]

The first accurate calculation of a molecular orbital wavefunction was that made by Charles Coulson in 1938 on the hydrogen molecule.[7] By 1950, molecular orbitals were completely defined as eigenfunctions (wave functions) of the self-consistent field Hamiltonian and it was at this point that molecular orbital theory became fully rigorous and consistent.[8]
3. Coulson, Charles, A. (1952). Valence. Oxford at the Clarendon Press.
4. Spectroscopy, Molecular Orbitals, and Chemical Bonding - Robert Mulliken's 1966 Nobel Lecture
5. Lennard-Jones Paper of 1929 - Foundations of Molecular Orbital Theory.
6. Hückel, E. (1934). Trans. Faraday Soc. 30, 59.
7. Coulson, C.A. (1938). Proc. Camb. Phil. Soc. 34, 204.
Hall, G.G. Lennard-Jones, Sir John. (1950). Proc. Roy. Soc. A202, 155.
8. Introduction to Molecular Orbital Theory - Imperial College London