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424 lines
9.0 KiB
ReStructuredText
424 lines
9.0 KiB
ReStructuredText
.. _module_hartree_fock:
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.. program:: hartree_fock
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.. default-role:: option
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============
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hartree_fock
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============
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The Hartree-Fock module performs *Restricted* Hartree-Fock calculations (the
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spatial part of the |MOs| is common for alpha and beta spinorbitals).
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The Hartree-Fock in an SCF and therefore is based on the ``scf_utils`` structure.
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It performs the following actions:
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#. Compute/Read all the one- and two-electron integrals, and store them in memory
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#. Check in the |EZFIO| database if there is a set of |MOs|. If there is, it
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will read them as initial guess. Otherwise, it will create a guess.
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#. Perform the |SCF| iterations
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The definition of the Fock matrix is in :file:`hartree_fock fock_matrix_hf.irp.f`
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For the keywords related to the |SCF| procedure, see the ``scf_utils`` directory where you will find all options.
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The main are:
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# :option:`scf_utils thresh_scf`
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# :option:`scf_utils level_shift`
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At each iteration, the |MOs| are saved in the |EZFIO| database. Hence, if the calculation
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crashes for any unexpected reason, the calculation can be restarted by running again
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the |SCF| with the same |EZFIO| database.
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The `DIIS`_ algorithm is implemented, as well as the `level-shifting`_ method.
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If the |SCF| does not converge, try again with a higher value of :option:`level_shift`.
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To start a calculation from scratch, the simplest way is to remove the
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``mo_basis`` directory from the |EZFIO| database, and run the |SCF| again.
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.. _DIIS: https://en.wikipedia.org/w/index.php?title=DIIS
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.. _level-shifting: https://doi.org/10.1002/qua.560070407
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EZFIO parameters
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----------------
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.. option:: energy
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Energy HF
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Programs
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--------
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* :ref:`scf`
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Providers
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---------
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.. c:var:: ao_two_e_integral_alpha
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File : :file:`hartree_fock/fock_matrix_hf.irp.f`
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.. code:: fortran
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double precision, allocatable :: ao_two_e_integral_alpha (ao_num,ao_num)
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double precision, allocatable :: ao_two_e_integral_beta (ao_num,ao_num)
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Alpha Fock matrix in AO basis set
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_coef_normalized_ordered_transp`
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* :c:data:`ao_expo_ordered_transp`
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* :c:data:`ao_integrals_map`
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* :c:data:`ao_integrals_threshold`
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* :c:data:`ao_nucl`
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* :c:data:`ao_num`
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* :c:data:`ao_overlap_abs`
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* :c:data:`ao_power`
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* :c:data:`ao_prim_num`
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* :c:data:`ao_two_e_integral_schwartz`
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* :c:data:`ao_two_e_integrals_in_map`
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* :c:data:`do_direct_integrals`
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* :c:data:`n_pt_max_integrals`
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* :c:data:`nucl_coord`
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* :c:data:`scf_density_matrix_ao_alpha`
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* :c:data:`scf_density_matrix_ao_beta`
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Needed by:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`hf_energy`
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.. c:var:: ao_two_e_integral_beta
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File : :file:`hartree_fock/fock_matrix_hf.irp.f`
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.. code:: fortran
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double precision, allocatable :: ao_two_e_integral_alpha (ao_num,ao_num)
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double precision, allocatable :: ao_two_e_integral_beta (ao_num,ao_num)
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Alpha Fock matrix in AO basis set
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_coef_normalized_ordered_transp`
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* :c:data:`ao_expo_ordered_transp`
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* :c:data:`ao_integrals_map`
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* :c:data:`ao_integrals_threshold`
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* :c:data:`ao_nucl`
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* :c:data:`ao_num`
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* :c:data:`ao_overlap_abs`
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* :c:data:`ao_power`
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* :c:data:`ao_prim_num`
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* :c:data:`ao_two_e_integral_schwartz`
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* :c:data:`ao_two_e_integrals_in_map`
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* :c:data:`do_direct_integrals`
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* :c:data:`n_pt_max_integrals`
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* :c:data:`nucl_coord`
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* :c:data:`scf_density_matrix_ao_alpha`
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* :c:data:`scf_density_matrix_ao_beta`
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Needed by:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`hf_energy`
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.. c:var:: extra_e_contrib_density
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File : :file:`hartree_fock/hf_energy.irp.f`
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.. code:: fortran
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double precision :: extra_e_contrib_density
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Extra contribution to the SCF energy coming from the density.
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For a Hartree-Fock calculation: extra_e_contrib_density = 0
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For a Kohn-Sham or Range-separated Kohn-Sham: the exchange/correlation - trace of the V_xc potential
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Needed by:
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.. hlist::
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:columns: 3
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* :c:data:`scf_energy`
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.. c:var:: fock_matrix_ao_alpha
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File : :file:`hartree_fock/fock_matrix_hf.irp.f`
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.. code:: fortran
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double precision, allocatable :: fock_matrix_ao_alpha (ao_num,ao_num)
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double precision, allocatable :: fock_matrix_ao_beta (ao_num,ao_num)
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Alpha Fock matrix in AO basis set
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_num`
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* :c:data:`ao_one_e_integrals`
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* :c:data:`ao_two_e_integral_alpha`
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Needed by:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao`
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* :c:data:`fock_matrix_mo_alpha`
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* :c:data:`fock_matrix_mo_beta`
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* :c:data:`scf_energy`
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.. c:var:: fock_matrix_ao_beta
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File : :file:`hartree_fock/fock_matrix_hf.irp.f`
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.. code:: fortran
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double precision, allocatable :: fock_matrix_ao_alpha (ao_num,ao_num)
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double precision, allocatable :: fock_matrix_ao_beta (ao_num,ao_num)
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Alpha Fock matrix in AO basis set
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_num`
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* :c:data:`ao_one_e_integrals`
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* :c:data:`ao_two_e_integral_alpha`
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Needed by:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao`
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* :c:data:`fock_matrix_mo_alpha`
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* :c:data:`fock_matrix_mo_beta`
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* :c:data:`scf_energy`
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.. c:var:: hf_energy
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File : :file:`hartree_fock/hf_energy.irp.f`
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.. code:: fortran
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double precision :: hf_energy
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double precision :: hf_two_electron_energy
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double precision :: hf_one_electron_energy
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Hartree-Fock energy containing the nuclear repulsion, and its one- and two-body components.
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_num`
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* :c:data:`ao_one_e_integrals`
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* :c:data:`ao_two_e_integral_alpha`
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* :c:data:`nuclear_repulsion`
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* :c:data:`scf_density_matrix_ao_alpha`
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* :c:data:`scf_density_matrix_ao_beta`
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.. c:var:: hf_one_electron_energy
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File : :file:`hartree_fock/hf_energy.irp.f`
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.. code:: fortran
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double precision :: hf_energy
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double precision :: hf_two_electron_energy
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double precision :: hf_one_electron_energy
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Hartree-Fock energy containing the nuclear repulsion, and its one- and two-body components.
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_num`
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* :c:data:`ao_one_e_integrals`
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* :c:data:`ao_two_e_integral_alpha`
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* :c:data:`nuclear_repulsion`
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* :c:data:`scf_density_matrix_ao_alpha`
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* :c:data:`scf_density_matrix_ao_beta`
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.. c:var:: hf_two_electron_energy
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File : :file:`hartree_fock/hf_energy.irp.f`
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.. code:: fortran
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double precision :: hf_energy
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double precision :: hf_two_electron_energy
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double precision :: hf_one_electron_energy
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Hartree-Fock energy containing the nuclear repulsion, and its one- and two-body components.
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ao_num`
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* :c:data:`ao_one_e_integrals`
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* :c:data:`ao_two_e_integral_alpha`
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* :c:data:`nuclear_repulsion`
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* :c:data:`scf_density_matrix_ao_alpha`
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* :c:data:`scf_density_matrix_ao_beta`
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Subroutines / functions
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-----------------------
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.. c:function:: create_guess:
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File : :file:`hartree_fock/scf.irp.f`
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Create a MO guess if no MOs are present in the EZFIO directory
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`ezfio_filename`
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* :c:data:`mo_coef`
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* :c:data:`mo_guess_type`
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* :c:data:`mo_one_e_integrals`
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* :c:data:`ao_ortho_lowdin_coef`
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* :c:data:`mo_label`
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Called by:
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.. hlist::
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:columns: 3
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* :c:func:`scf`
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Calls:
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.. hlist::
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:columns: 3
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* :c:func:`ezfio_has_mo_basis_mo_coef`
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* :c:func:`huckel_guess`
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* :c:func:`mo_as_eigvectors_of_mo_matrix`
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Touches:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`mo_coef`
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* :c:data:`mo_label`
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.. c:function:: run:
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File : :file:`hartree_fock/scf.irp.f`
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Run SCF calculation
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Needs:
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.. hlist::
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:columns: 3
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* :c:data:`scf_energy`
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* :c:data:`mo_label`
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Called by:
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.. hlist::
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:columns: 3
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* :c:func:`pt2`
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* :c:func:`scf`
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Calls:
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.. hlist::
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:columns: 3
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* :c:func:`ezfio_set_hartree_fock_energy`
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* :c:func:`roothaan_hall_scf`
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Touches:
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.. hlist::
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:columns: 3
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`fock_matrix_ao_alpha`
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* :c:data:`mo_coef`
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* :c:data:`level_shift`
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* :c:data:`mo_coef`
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