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229 lines
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ReStructuredText
229 lines
12 KiB
ReStructuredText
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=============================
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The Documentation of the code
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=============================
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The heart of the problem : how do we compute the perturbation ?
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===============================================================
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In this section we will present the basic ideas of how do we compute any kind of perturbative quantity.
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The main problem
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^^^^^^^^^^^^^^^^
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Consider a simple problem of perturbation theory in which you have a *general* multireference wave function :math:`| \psi \rangle`
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(no trivial way to know the kind of relations between those determinants) :
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.. math::
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| \psi \rangle = \sum_{I=1,N_{det}} c_I | D_I \rangle
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and you would like to compute its second order :term:`perturbative energetic correction`, which we can write like this for the sake of simplicity:
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.. math::
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E_{PT2} = \sum_{P \, \rm{that} \, \rm{are} \, \rm{not} \, \rm{in} \, | \psi \rangle } \frac{\langle \psi | H | D_P \rangle^2}{\Delta E_P}
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and the :math:`\Delta E_P` will determine what kind of PT you use. Note that you must not double count a determinant :math:`| D_P \rangle` and that you must not count those which are in :math:`| \psi \rangle`.
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What you have to do is to apply the :math:`H` operator on this :math:`| \psi \rangle` that would generate a lot of determinants :math:`|D \rangle`,
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and you must find a way to see if :
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#) the determinant :math:`|D \rangle` is in :math:`| \psi \rangle`
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#) the determinant :math:`|D \rangle` have already been counted
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How do we do in practice ? We apply :math:`H` succesively on each determinant of :math:`| \psi \rangle` and each :math:`H` application generates a lot of determinant :math:`|D \rangle`. For each determinants :math:`|D \rangle` we check with a very optimized subroutine if
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#) :math:`|D\rangle` was a single or a double excitation respect to all the determinant on which we previously applyed :math:`H`
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:math:`\Rightarrow` if it is the case then it have already been computed in the past and so we don't double count it.
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#) :math:`|D\rangle` is already in the rest of the :math:`| \psi \rangle`
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:math:`\Rightarrow` if it is the case you must not count it.
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This subroutine (:samp:`connected_to_ref` ) is called a **HUGE** number of times and so it have been optimized in a proper way.
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Its basis is the :samp:`popcnt` hardware instruction that figures in the :samp:`SSE4.2` releases of processors.
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It allows to know how many bites are set to one in an integer within a few cycles of CPU.
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By manipulation of bits masks you can easily extract the excitation degree between two determinants.
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One interesting feature of this approach is that it is easily and efficiently parallelizable (which of cours have been done),
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and you can easily reach an parallel efficiency of about :math:`95\%`.
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The link between the perturbation and the selection
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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In the selected CI algorithm you have general :math:`| \psi \rangle` multi determinantal wave function and you want to make it better
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by proposing some new candidates to enter in this wave function.
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Those candidates must of course not be already in :math:`| \psi \rangle` and since their are selected thanks to their perturbative properties (on the energy or on the coefficient), their are generated through some application of the :math:`H` operator. So we see that we have exactly the same kind of feature than in the perturbation.
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How do we select the determinant in practice ? Exactly like we do the perturbation !
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do G = 1, :term:`N_{Generators}`
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#) We apply :math:`H` on one :term:`generators`
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:math:`\Rightarrow` :math:`H|D_G \rangle = \sum_D \langle D | H |D_G \rangle |D \rangle`
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#) For each determinant :math:`|D \rangle` we check if it could have been generated from previous :term:`generators` :math:`| D_{G'} \rangle`
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:math:`\Rightarrow` If it is not the case we check if it belongs to :math:`| \psi \rangle`
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#) We compute its perturbative property
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#) If it is important we put it in a buffer of the potential candidates to the new set of :term:`internal determinants`
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#) go to 1
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enddo
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So once you have applyed :math:`H` on all the :term:`generators`, you sort all the buffer of the candidates by their importance,
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and after you pick up the most important ones, which will enter in the wave function and be diagonalized.
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Just to be more precise, what we drescribe here is the standard CIPSI algorithm (which :term:`target space` is always the FCI). In practice, if you replace the :math:`H` operator by the :term:`restricted H operator` defined by the :term:`target` space you have exactly what is emplemented.
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The typical feature of an iteration
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===================================
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An iteration of the selected CI program is always built in the same way. This can be resumed in the following simple tasks.
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Iteration :
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#) :term:`restricted H operator` applyed on the :term:`generators`
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:math:`\Rightarrow` :term:`perturbativ action` (*e.g* Selection of some :term:`perturbers`, calculation of the :math:`E_{PT2}^m`, etc ...)
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#) Some update induced by the :term:`perturbative action` (*e.g* diagonalization of the new :math:`H` matrix, etc ...)
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#) Check the :term:`stopping criterion`
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#) Update the :term:`generators` subset
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#) Save restart data if needed
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#) Iterate
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To go into details we list the various available options for each task.
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The :samp:`restricted_H_apply` like subroutines
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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Here we enter into details on the part of the subroutines that is responsible for the :term:`restricted H operator` part of the tasks.
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The general ideas
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^^^^^^^^^^^^^^^^^
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This subroutine takes in input a determinant (in term of an integer key) and some bits masks
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that are used to restrict the excitations (see the :term:`excitations bits masks` and :term:`excitations restrictions`).
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It generates the singles and doubles excitations from the input determinant and these :term:`excitations bits masks`.
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This subroutine will be applyed on the :term:`generators` determinants to generate the :term:`perturbers`.
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This subroutine in itself does not exist, it is just a skeleton that generates all possible singles and doubles.
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As seen in the previsous section, once you apply :math:`H` on a given determinant, you will use the generated determinants
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to do a certain number of things that deal with in general a perturbative quantity, this is the :term:`perturbative action`.
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A way to resume what is done in the subroutine and to make a mental representation can be explained like this :
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.. code-block:: fortran
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subroutine restricted_H_apply(key_in)
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do i = 1, available_holes(1)
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do j = 1, available_holes(2)
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do k = 1, available_particles(1)
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do l = 1, available_particles(2)
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! you generate some excitations on key_in that will generate some key_out
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call excitation(i,j,k,l,key_in,key_out)
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! you exploit key_out to do some perturbative work
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call perturbative_action(key_out)
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enddo
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enddo
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enddo
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enddo
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end
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So we see that here once we have made an excitation on :samp:`key_in` that generates :samp:`key_out`,
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we can do some work related to the :term:`perturbative action` on this :samp:`key_out`.
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In this simple representation of the subroutine, there are some :samp:`available_holes` and :samp:`available_particle`.
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This is due to the :term:`excitation restrictions` that are implicitly defined by the :term:`target space`,
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and to the :term:`restricted orbitals` that are defined by the user.
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In practice those :term:`excitation restrictions` are just the excitations that are going to be allowed to a given :term:`generator determinant`.
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We do this by using some :term:`excitations bits masks`.
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The :term:`excitation restrictions` and the :term:`restricted orbitals` are built thanks to the use of :term:`excitations bits masks`.
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Available :term:`excitation restrictions`
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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The :term:`excitation restrictions` prohibits some kind of excitations because it is in the definition
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of the :term:`target space` to avoid a certain class of excitation.
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For instance, in the :term:`CAS+DDCI` method, you will apply all the single and double excitations on the top of the :term:`CAS wave function`.
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After those :term:`excitation restrictions` defined by the :term:`target space`, there can be some kind of excitations that the user wishes to avoid.
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For instance, within a :term:`CISD` or a :term:`CAS+DDCI` you can wish that all the excitations of the core electrons can be neglected,
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or that there are some virtuals that are not relevant for a certain kind of correlation effects.
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This restrictions are done in the program by defining some classes of orbitals that depend both on the method you would like to use,
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and by the specific restrictions you would like to do on the top of that. So we see that there are classes of orbitals that depend on the method,
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and other classes that can be defined for any class of method.
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This classes are the the :term:`frozen occupied orbitals` and the :term:`deleted virtual orbitals` .
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Available :term:`perturbative action`
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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From what we saw previously, when an excitation is performed on a given :term:`generator`,
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depending on the method defined by the user, different actions can be performed at that point of the calculation.
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Nevertheless, all this actions here deal with the perturbation, that is why we called this step the :term:`perturbative action`.
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The :term:`perturbative action` is very flexible. It consists in doing (or not) a certain kind of things.
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When a given determinant :samp:`key_out` is generated, you can :
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#) check if this determinants have to be taken into account (see :samp:`connected_to_ref` and :samp:`is_in_ref`)
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#) compute its :term:`perturbative energetic contribution` and its :term:`perturbative coefficient` (see :term:`perturbation theory`)
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#) use those perturbative quantities to do something that deals with it (see :term:`perturbative possibility` )
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In principle, for each of those actions one would put a :samp:`if` statement and decline all the possible actions to do.
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However, because there can exist a *lot* of possible action and because this loop is really intern, putting a lot of :samp:`if` statement
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is not a good idea and will slow the code.
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To avoid that we generate with a python script all possible subroutines corresponding to some actions, and the program will use the one
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that will be defined by the method desired by the user. In this way there is no unnecessary tests in the intern loop, it done in the input.
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The :term:`perturbative possibility`
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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Once you have compute the :term:`perturbative energetic contribution` and the :term:`perturbative coefficient` of a given :term:`perturber`,
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you must use those quantities. Here is listed what is available :
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#) accumulate it :term:`perturbative energetic contribution` to compute the :term:`Energetic perturbative correction`
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#) accumulate it :term:`perturbative coefficient` to compute the :term:`first order perturbative norm`
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#) put or not the :samp:`key_out` determinant in a buffer to select some new :term:`intenal determinants` see :term:`selection`
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#) update the arrays of the :term:`correlation energy by holes and particles` (see :term:`CISD+SC2`)
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#) dress all the diagonal matrix elements of the :term:`internal determiants` (see :term:`Dressed MRCI`)
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Connected to ref / is in ref
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^^^^^^^^^^^^^^^^^^^^^^^^^^^^
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This subroutine takes in input a determinant (in term of an integer key), an array of determinants :samp:`keys` (containing :samp:`N_det` determinants)
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and an integer :samp:`i_past` which is smaller or equal to :samp:`N_det`.
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It checks if the input determinant is connected by the :math:`H` matrix to all the determinants in :samp:`keys` that are before :samp:`i_past`.
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It also check if the input determinant is in the whole list of determinants :samp:`keys`.
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In output you have an integer :samp:`c_ref` that have the following values :
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#) 0 : the input determinant is not in :samp:`keys` and is not connected to any determinant
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in :samp:`keys` that is before :samp:`i_past`.
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#) +m : the input determinant is connected by the :math:`H` matrix to the *m* th determinant :samp:`keys`.
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#) -m : the input determinant is already in :samp:`keys` and it is the *m* th determinant in :samp:`keys`
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