===================================== Selection, perturbation ... keywords ===================================== .. |CISD| replace:: :abbr:`CISD (Configuration Interaction with Single and Double excitations)` .. |HF| replace:: :abbr:`HF (Hartree Fock)` .. |CAS-CI| replace:: :abbr:`CAS-CI (Complete Active Space Configuration Interaction)` .. |DDCI| replace:: :abbr:`DDCI (Difference Dedicated Configuration Interaction)` .. glossary:: :sorted: Energetic perturbative correction Corresponds to the correction to the energy at the second order of a given perturbtation theory to a given state m. By convention it noted :math:`E_{PT2}^m` Variational energy Corresponds to the variational energy of the :term:`selected wave function` for a given state . By convention it noted :math:`E_{Var}^m` for the mth eigenvector. .. math:: E_{Var}^m = \langle \psi_m |H|\psi_m \rangle Estimated target energy Corresponds to the estimation of the target energy for a given :term:`selected wave function` and a given state. By convention it noted :math:`E_{Target}^m`. Its mathematical expression is : .. math:: E_{Target}^m = E_{Var}^m + E_{PT2}^m Selected wave function Corresponds to the wave function that have been previously selected for a given state m at a current iteration. This wave function is defined by the set of the :term:`internal determinants` and by their coefficients on the state m. By convention it is noted :math:`|\psi_m\rangle` .. math:: | \psi_m \rangle = \sum_{I=1,N_{selected}} c_I^m | D_I \rangle EN EG Stands for Eipstein Nesbet with EigenValues zeroth order energy perturbation theory. It is a state specific 2nd order perturbation theory. Here m is the index of the eigenstate. The :math:`H_0` of this PT is defined as the diagonal part of the Hamiltonian such as the :math:`E_m` is equal to the average value of the Hamiltonian on the :term:`selected wave function` and the :math:`E_P` is equal to the average value of the Hamiltonian on the :term:`perturbers` This perturbation have bad formal properties but some nice numerical features of convergence. From the definition, one get the first order coefficient and its related second order energetic contribution of a a perturber : .. math:: c_{D_P}^m= \sum_{S=1,N_{\rm selectors}} \frac{c_S^m \langle D_S|H|D_P\rangle}{ \langle \psi_m |H|\psi_m \rangle - \langle D_P|H| D_P \rangle } \\ e_{D_P}^m= \frac{(\sum_{S=1,N_{\rm selectors}} c_S^m \langle D_S|H|D_P\rangle)^2}{\langle \psi_m |H|\psi_m \rangle - \langle D_P|H| D_P \rangle } Stopping criterion Condition decided by the user to stop the calculation. This criterion might be on the :term:`Energetic perturbative correction`, on the number of :term:`internal determinants` N_selected_max or on the stability of the :term:`estimated target energy` The user can also send a Ctrl+C to stop the calculation, and it will kill itself properly, saving the datas that need to be saved. Target wave function Wave function of the :term:`target space` Target space Target of the CI calculation. Defining a method (CISD, CAS-CI and so on) is equivalent to define the :term:`target space`. The target space defines the rules to define the :term:`Generators` , the rules of the :term:`excitation restrictions`, and the perturbation theory to be used. There are two type of methods/:term:`target space` proposed in the code : #) the CAS-CI type methods where you do not restrict any kind of excitation degree within a given list of orbitals. #) the singles and doubles excitations on the top of a given reference wave function (:term:`CISD`, :term:`CISD+SC2`, :term:`CAS+SD`, :term:`CAS+DDCI`, :term:`CAS+MRPT2`) Their is a great difference between those two types of method in the way it is implemented. In the CAS-CI method, when you have chosen an :term:`active space` (so a list of orbitals and electrons to make a FCI within this active space), all the :term:`Internal determinants` that have been selected and that form the :term:`selected wave function` can potentially be part of the :term:`generators`, by mean that the :term:`restricted H operator` could be potentially applyed on all the :term:`internal determinants` to generate some other :term:`perturbers`. In the singles and doubles excitation on the top of a given reference wave function, the subset of :term:`generators` and so the rules to recognize them, is fixed at the begining of the method. Those :term:`generators` are precisely all the determinants forming the :term:`reference wave function`. There are the different :term:`target space` that are available : #) :term:`CISD` #) :term:`CISD+SC2` #) :term:`CASCI` #) :term:`CASCI+S` #) :term:`CASCI+SD` #) :term:`CASCI+DDCI` #) :term:`CASCI+DDCI+(2h-2p)PT2` #) :term:`CAS-CI+MRPT2` Target energy Energy of the target space. H operator Hamiltonian operator defined in terms of creation and anihilation operators in the spin orbital space. Excitation restrictions Restriction in the :term:`H operator` that the user imposes to define the target sapce. For example : 1) If one freeze some core orbitals or delete some virtuals, it is an :term:`excitation restrictions` 2) If one prohibits the pure inactive double excitations in a CAS+SD one get a DDCI 3) any kind of restriction in the full application of the :term:`H operator` Restricted H operator :term:`H operator` taking into account the :term:`Excitation restrictions` CISD+SC2 Method developped by JP. Malrieu that can be seen as a cheap approximation of the CCSD. It makes a CISD size consistant and separable for closed shell systems. It is based on a CISD calculation where the diagonal part of the H matrix is dressed by the repeatable correlation energy previsously obtained. So it is a CISD dressed by the disconnected triples and quadruples. Generators Set of generator determinants. By convention a generator is written as :math:`|D_G\rangle` . A generator determinant is a determinant on which the :term:`restricted H operator` is being applied for the selection and/or the perturbation. Internal determinants Selected determinants in terms of integers keys. By convention an Internal determinant is written as :math:`|D_I\rangle` . By convention, the :term:`Generators` are at the begining of the array. Intern space Set of all the :term:`internal determinants`. Perturbers Determinants within the :term:`target space` but taht are not already included in the :term:`intern space`. They are created from the :term:`Generators` that belongs :term:`Intern space` for a given :term:`selected wave function`. By convention a perturber is written as :math:`|D_P\rangle`. Selectors Determinants that are used to compute the perturbative properties of the :term:`perturbers`. By convention a selector is written as :math:`|D_S\rangle` . The selectors are a subset of determinant of the total wave function (that is the :term:`Internal determinants`). This subset contains at least the :term:`Generators` determinants. The perturbative properties (energy, coefficient or else) of the :term:`perturbers` are calculated on all the :term:`selectors` :math:`|D_S\rangle` .. math:: c_{D_S}= \sum_{S=1,N_{\rm selectors}} \frac{c_S\langle D_S|H|D_P\rangle}{\Delta E_{P,S}} \\ e_{D_S}= \frac{(\sum_{S=1,N_{\rm selectors}} c_S \langle D_S|H|D_P\rangle) ^2}{\Delta E_{P,S}}