Electronic Structure of Carbon Monoxide

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Abstract
The LCAO—MO SCF orbitals for carbon monoxide have been calculated with 1s, 2s, and 2p Slater atomic functions, using best atom (Roothaan) exponents. All atomic integrals have been calculated. While all the orbitals are orthogonal, the inner shells have been given a fixed form. The calculated binding energy (using these SCF orbitals for the molecular energy and the same atomic functions for atomic energy) is about 40% of that observed. A limited configuration interaction calculation gives about 55% of the observed binding energy. Both the single determinant and the CI wave function predict a dipole moment which is in agreement with the observed sign C—O+, but the error in magnitude is rather large. The atomic populations suggest the sign of the dipole moment to be C+O—, in agreement with Malone's rule. The ionization energies have been calculated and the agreement with experiment is very satisfactory. Some of the observed lower electronic transitions can be understood by using single configurations constructed from these SCF orbitals, but, before a more complete analysis of the spectrum can be attempted, it may be necessary to introduce atomic functions from the M shell.

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