LCAO Self-Consistent Field Calculation of the Ground State of Carbon Dioxide
- 1 March 1951
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 19 (3) , 347-362
- https://doi.org/10.1063/1.1748208
Abstract
LCAO molecular orbitals and ionization potentials have been calculated for the ground state of CO2 using Roothaan's LCAO self‐consistent field method. The interactions of all electrons have been explicitly considered, and no extra‐geometrical empirical data have been used. The calculated molecular orbitals are in general agreement with those predicted by Mulliken and Moffitt from semi‐empirical considerations. The calculated ionization energies are 11.5 ev for a 1π g electron and 17.9 ev for a 2σ u electron, compared with the experimental 13.8 ev, and 18.0 ev, respectively. The evaluation of the large number of integrals over atomic orbitals that occur, is discussed in an appendix. All the larger integrals were calculated exactly, the smaller ones approximated. Useful approximation methods for some of these integrals are considered.Keywords
This publication has 59 references indexed in Scilit:
- Polar structures in the theory of conjugated molecules I. Identification of the ethylene π-electron statesProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1950
- The electronic structures of carbon monoxide and carbon dioxideProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1949
- Molecular orbitals arid the Hartree fieldProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1949
- Correlated Molecular Orbitals1Journal of the American Chemical Society, 1948
- Repulsive Forces in Relation to Bond Energies, Distances and Other PropertiesJournal of the American Chemical Society, 1948
- A note on the criterion of maximum overlapping of wave functionsMathematical Proceedings of the Cambridge Philosophical Society, 1937
- Über das Dreizentrenproblem. IThe European Physical Journal A, 1935
- The Electronic Structure ofMathematical Proceedings of the Cambridge Philosophical Society, 1935
- A theoretical investigation of the oxygen atom in various states of ionisationProceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character, 1933
- THE NATURE OF THE CHEMICAL BOND. APPLICATION OF RESULTS OBTAINED FROM THE QUANTUM MECHANICS AND FROM A THEORY OF PARAMAGNETIC SUSCEPTIBILITY TO THE STRUCTURE OF MOLECULESJournal of the American Chemical Society, 1931