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Why are Coupled-Cluster and MBPT Energies not Variational?

      Electron correlation methods other than CI may not be variational. For example, consider the coupled-cluster energy expression
 equation684
If the operator tex2html_wrap_inline3685 is not trunctated, then we know that tex2html_wrap_inline3687. Generally, however, the operator is truncated. Let us define tex2html_wrap_inline3689 for our truncated tex2html_wrap_inline3691. Now define tex2html_wrap_inline3693. Note that in general tex2html_wrap_inline3695, which would have occured had we used tex2html_wrap_inline3697 on the left. Then the energy expression is
 equation709
which, after expansion over the complete set of eigenvectors, becomes
 equation715
This simplifies to
equation723
At this point we can go no farther, because the terms tex2html_wrap_inline3699 may be negative, in contrast to the situation in equation (3.12).

For completeness, we also show that MBPT energies are not variational. The nth order MBPT wavefunction may be written [13] as
equation731
where the sum is over ``linked diagrams'' only. The nth order energy is then given by
equation744
Since this integral is not symmetric, the energy is not variational. Only the first-order perturbation theory energy (which is also the Hartree-Fock energy) is variational, since it uses tex2html_wrap_inline3705.    



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