Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published May 1, 1949 | public
Journal Article Open

The Valence-State Energy of the Bivalent Oxygen Atom

Pauling, Linus

Abstract

A significant simplification in the discussion of the structure of molecules can be achieved by referring the energies of molecules not to the energies of their constituent atoms in any one of the stationary spectroscopic states of the isolated atoms, but instead to a hypothetical valence state of each atom. [1] The valence state of an atom is defined as that state in which it has the same electronic structure as it has in the molecule. Thus in the valence state the spins of the electrons that are used for forming bonds in a molecule are considered to resonate between positive and negative values, corresponding to the resonance of each bofiding electron with another electron of opposite spin in the atom with which the bond is formed. For the bivalent oxygen atom, with six L electrons, two orbitals, one mainly 2s in character and one 2p, are occupied by unshared pairs, and the other two orbitals, mainly 2p but with a small amount of s hybridization, are occupied by one bonding electron apiece, the spins of which are parallel 50 per cent of the time and antiparallel 50 per cent of the time. In the following paragraphs values of the energy of this bivalent state of the oxygen atom relative to the normal state of the isolated atom, 3P, are derived by four different methods. It is found that the four values agree reasonably well with one another, and their average value, 0.74 v.e., is indicated to be reliable to about 0.05 v.e.

Additional Information

Copyright © 1949 by the National Academy of Sciences Communicated March 21, 1949 Contribution No. 1283 from the Gates and Crellin Laboratories of Chemistry.

Files

PAUpnas49b.pdf
Files (438.2 kB)
Name Size Download all
md5:168235d4fd569d1cfba35b51a13f7120
438.2 kB Preview Download

Additional details

Created:
August 21, 2023
Modified:
October 16, 2023