The Multiconfiguration Hartree-Fock Method for Atomic Energy Levels and Transition Probabilities
The effect of correlation in the motion of electrons in a many electron system is an important factor in the theoretical determination of atomic properties. When Hartree1 derived his equations, he assumed the electrons moved in the field of the nucleus screened by the spherically averaged distribution of all the other electrons. Thus the effect of correlation in the motion of electrons was neglected. In fact, in his model there was a finite probability that two electrons might occupy the same region of space. Later Fock2 modified these equations. Starting with an antisymmetric total wavefunction and applying a variational procedure, he obtained what Hartree called the “equations with exchange” now referred to as the Hartree-Fock (HF) equations. Electrons with the same spin co-ordinates are repelled in this model but other correlation effects remain. For reasons such as these, Löwdin3 defined the error in the HF approximation as the correlation error.
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