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.. _dscf:
===========================
Delta Self-Consistent Field
===========================
--------------------------------------------
Linear expansion Delta Self-Consistent Field
--------------------------------------------
The method of linear expansion Delta Self-Consistent Field \ [#delscf]_
adds the density of a specified orbital `\varphi_a(r)` to the
total density in each step of the self-consistency cycle. The extra charge
is usually taken from the fermi level to keep the system neutral:
.. math::
n(r) = \sum_nf_{N-1}(T,\varepsilon_n)|\varphi_n(r)|^2 + |\varphi_a(r)|^2.
with `N` being the total number of electrons and `f_{N-1}(T,\varepsilon_n)`
is the Fermi-Dirac distribution of the `N-1` electron system . To get the
band energy right `\varphi_a(r)` needs to be expanded in Kohn-Sham orbitals:
.. math::
|\varphi_a\rangle = \sum_nc_{na}|\varphi_n\rangle,
\qquad c_{na} = \langle\varphi_n|\varphi_a\rangle
and the band energy of the orbital becomes
.. math::
\varepsilon_a = \sum_n|c_{na}|^2\varepsilon_n.
The method is a generalization of traditional Delta Self-Consistent Field
where only the occupation numbers are modified and it will reduce to that,
if only one (normalized) term is included in the expansion of `\varphi_a(r)`.
----------------
Simple molecules
----------------
The example below calculates the excitation energy of the
`5\sigma\rightarrow2\pi` transition in CO. We only specify that the
`2\pi` orbital should be occupied ([[1.0, lumo, 1]] means 1.0 electrons
in lumo with spin 1) and the method will take the electron from highest
occupied orbital which in this case is `5\sigma`.
The lumo is an instance of the class AEOrbital which calculates the
expansion of the saved `2\pi` state in each iteration step.
In order to obtain the all-electron overlaps `\langle\varphi_n|2\pi\rangle`
we need to supply the projector overlaps in addition to the
pseudowavefunction.
Exciting the LUMO in CO (:download:`co.py`):
.. literalinclude:: co.py
The commented lines ``lumo = dscf.Molecular...``
uses another class to specify the `2\pi` orbital of CO which does not require
a ground state calculation of the molecule. In the simple example above the
two methods give identical results, but for more complicated systems the
AEOrbital class should be used \ [#des]_. When using the AEOrbital class
a new calculator object must be constructed for the dscf calculation.
In the example above we only specify a single state, but the function
``dscf.dscf_calculation`` takes a list of orbitals as input and we could for
example have given the argument [[1.0, lumo, 1], [-1.0, pi, 0]] which would
force the electron to be taken from the `\pi` orbital with spin 0. The pi
should of course be another instance of the AEOrbital class.
---------------------
Exciting an adsorbate
---------------------
The method of linear expansion Delta Self-Consistent Field was designed
for calculations with strongly hybridized orbitals. For example molecules
chemisorbed on transition metals. In such cases the
traditional Delta Self-Consistent Field breaks down since the orbital
to be occupied is no longer well described by a single Kohn-Sham state.
The script :git:`~doc/documentation/dscf/homo.py` calculates
the HOMO energy of CO adsorbed on-top Pt(111). The script starts
from scratch, but usually one would start from an optimized configuration
saved in a file ``gs.gpw``. The script only calculates the total energy of
the excited state so the excitation energy is obtained as the difference
between ground and excited state energies.
First a calculation of gas-phase CO is performed and the
HOMO pseudo-wavefunctions and the projector overlaps are saved. The
energy range [-100.0, 0.0] means we only include states below the Fermi
level (default is states above).
The script :git:`~doc/documentation/dscf/lumo.py` calculates
the LUMO energy of the same system, but is slightly more complicated due to
the degeneracy of the `2\pi` orbital. We would like to occupy the `2\pi_y`
orbital and we need to figure out which band (5 or 6) this orbital
corresponds to in each k-point before we start the slab calculation.
.. [#delscf] J. Gavnholt, T. Olsen, M. Engelund and J. Schiøtz,
Delta Self-Consistent Field as a method to obtain potential
energy surfaces of excited molecules on surfaces,
*Phys. Rev. B* **78**, 075441 (2008)
.. [#des] T. Olsen, J. Gavnholt and J. Schiøtz,
Hot electron mediated desorption rates calculated from excited
state potential energy surfaces,
*Phys. Rev. B* **79**, 035403 (2009)
|
