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qp2/docs/source/users_guide/natural_orbitals.rst
2019-03-07 18:24:38 +01:00

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Natural orbitals
================
Summary
-------
To produce state-average natural orbitals, run ::
qp_run save_natorb file.ezfio
The |MOs| will be replaced, so the two-electron integrals and the wave
function are invalidated as well.
Extracting natural orbitals
---------------------------
Once obtained the near |FCI| wave function, one can obtain many
quantities related to it. One of these quantities are the natural
orbitals which have the property of diagonalizing the one-body
density matrix:
.. math::
\rho_{ij} = \delta_{ij}
where the element of the one-body density matrix :math:`\rho_{ij}` is
defined as:
.. math::
\rho_{ij} = \langle \Psi | \left( a^{\dagger}_{j,\alpha} a_{i,\alpha} + a^{\dagger}_{j,\beta} a_{i,\beta} \right) | \Psi \rangle
These orbitals are in general known to be better than the usual |HF|
|MOs| as they are obtained from a correlated wave function. To use these
orbitals for future calculations, one has to replace the current |MOs|
by the natural orbitals. To do so, just run:
.. code::
qp_run save_natorb file.ezfio
Hands on
--------
.. important::
As the |MOs| are changed, for the sake of coherence of future
calculations, the :ref:`save_natorb` program *automatically removes the
current wave function* stored in the |EZFIO| database and replaces
it by a single Slater determinant corresponding to a |HF| occupation
of the new spin orbitals. Also, all the keywords to read the one-
and two-electron integrals on the |MO| basis are set to ``None`` in
order to be sure to avoid reading integrals incompatible with the
current set of |MOs|.
.. seealso::
The documentation of the :ref:`save_natorb` program.