diff --git a/Notes_CSF/Theory_CFG_CIPSI.org b/Notes_CSF/Theory_CFG_CIPSI.org index 089e296c..511af0d1 100644 --- a/Notes_CSF/Theory_CFG_CIPSI.org +++ b/Notes_CSF/Theory_CFG_CIPSI.org @@ -1,11 +1,14 @@ #+TITLE: CFG CIPSI -#+AUTHOR: Vijay Gopal Chilkuri (vijay.gopal.c@gmail.com) +#+AUTHOR: Vijay Gopal Chilkuri +#+EMAIL: vijay.gopal.c@gmail.com #+DATE: 2020-12-08 Tue 08:27 #+startup: latexpreview +#+STARTUP: inlineimages + #+LATEX_HEADER: \usepackage{braket} -* Biblio +* Biblio * Theoretical background Here we describe the main theoretical background and definitions of the @@ -14,7 +17,7 @@ definitions of the overlap, one-particle, and two-particle matrix-elements. Finally, an algorithm is presented for the sigma-vector (\( \sigma \)-vector defined later) calculation using the CFG basis. - + ** Definitinon of CI basis @@ -41,7 +44,7 @@ \(\ket{^S\Phi_i}\). The coefficients \(O^b_{a,k}\) depend only on the number of SOMOs in \(\Phi_i\). - + Each CFG contains a list of CSFs related to it which describes the spin part of the wavefunction (see Eq: [[Eq:definebasis3]]) which is encoded in the BFs as shown below in Eq: [[Eq:definebasis5]]. @@ -52,7 +55,7 @@ \ket{^S\Phi_i} = \left\{ \ket{^S\Phi^1_i}, \ket{^S\Phi^2_i}, \dots, \ket{^s\Phi^{\Ncsf}_i} \right\} \end{equation} - + #+NAME: Eq:definebasis4 \begin{equation} @@ -130,52 +133,52 @@ The matrix-element (ME) evaluation follows a similar logic as the evalulation of the overlap. However, here the metric is the one-, or two-particle operator \(\hat{E}_{pq}\) or \(\hat{E}_{pq}\hat{E}_{rs}\) as shown in Eq: [[Eq:defineme1]] and Eq: [[Eq:defineme2]]. - + #+NAME: Eq:defineme1 \begin{equation} \braket{^S\Phi^k_i|\hat{O}_{pq}|^S\Phi^l_j} = \left( C_{i,1} \right)^{\dagger} \mathbf{O}_i\cdot\mathbf{A}^{pq}_{ij}\cdot\mathbf{O}_j C_{j,1} \end{equation} - + #+NAME: Eq:defineme2 \begin{equation} \braket{^S\Phi^k_i|\hat{O}_{pq,rs}|^S\Phi^l_j} = \sum_K \left( C_{i,1} \right)^{\dagger} \mathbf{O}_i\cdot\mathbf{A}^{pq}_{ik}\cdot\mathbf{O}_k \mathbf{O}_k\cdot\mathbf{A}^{rs}_{kj}\cdot\mathbf{O}_j C_{j,1} \end{equation} - - Where, \(\hat{O}_{pq}\) and \(hat{O}_{pq,rs}\) represent an arbitrary one-, and - two-particle operators respectively. Importantly, the one-, and two-particle - matrix-element evaluation can be recast into an effecient matrix multiplication - form which is crucial for a fast evaluation of the action of the operators + + Where, \(\hat{O}_{pq}\) and \(hat{O}_{pq,rs}\) represent an arbitrary one-, and + two-particle operators respectively. Importantly, the one-, and two-particle + matrix-element evaluation can be recast into an effecient matrix multiplication + form which is crucial for a fast evaluation of the action of the operators \(\hat{O}_{pq}\) and \(hat{O}_{pq,rs}\). The matrix \(\mathbf{A}^{pq}_{ij}\) contains - the result of the operation \(\braket{^S\Phi^k_i|\hat{O}_{pq}|^S\Phi^l_j}\) in terms + the result of the operation \(\braket{^S\Phi^k_i|\hat{O}_{pq}|^S\Phi^l_j}\) in terms of BFs and is therefore of size \(NCSF(i) \textit{x} NBF(i)\). In this formulation, the determinant basis is entirely avoided. Note that the size and contents of the matrix \(\mathbf{A}^{pq}_{ij}\) depends only on the total number of SOMOs and the total spin \(S\), therefore, an optimal prototyping scheme can be deviced for a rapid calculaiton of these matrix contractions. - The resolution of identity (RI) is used to evaluate the two-particle operator since - this alleviates the necessacity to explicity construct two-particle matrix-elements + The resolution of identity (RI) is used to evaluate the two-particle operator since + this alleviates the necessacity to explicity construct two-particle matrix-elements \(\braket{^S\Phi^k_i|\hat{O}_{pq,rs}|^S\Phi^l_j}\) directly. - + ** Sigma-vector evaluation Once the \(\mathbf{A}^{pq}_{ij}\) matrices have been constructed for the given selected list of CFGs, the prototype lists for the \(\mathbf{A}^{pq}_{ij}\) matrices - can be constructed. Following this, one can proceede to the evaluation of the sigma-vector - as defined in the Eq [[Eq:definesigma1]]. - - + can be constructed. Following this, one can proceede to the evaluation of the sigma-vector + as defined in the Eq [[Eq:definesigma1]]. + + #+NAME: Eq:definesigma1 \begin{equation} - \sigma = \sum_{pq} \tilde{h}_{pq}\hat{E}_{pq}|\ket{^S\Phi^l_j} + \frac{1}{2}\sum_{pq,rs} g_{pq,rs} \hat{E}_{pq}\hat{E}_{rs}|\ket{^S\Phi^l_j} + \sigma = \sum_{pq} \tilde{h}_{pq}\hat{E}_{pq}|\ket{^S\Phi^l_j} + \frac{1}{2}\sum_{pq,rs} g_{pq,rs} \hat{E}_{pq}\hat{E}_{rs}|\ket{^S\Phi^l_j} \end{equation} - + The one-electron part of the sigma-vector can be calculated as shown in Eq: [[Eq:defineme1]] - and the two-electron part can be calculated using the RI as shown in Eq: [[Eq:defineme2]]. + and the two-electron part can be calculated using the RI as shown in Eq: [[Eq:defineme2]]. The most expensive part involves the two-particle operator as shown on the RHS of Eq: [[Eq:definesigma1]]. In this CFG formulation, the cost intensive part of the sigma-vector evaluation has been recast into an efficient BLAS matrix multiplication operation. Therefore, this formulation is the most efficient albeit at the cost of storing the prototype matrices \(\mathbf{A}^{pq}_{ij}\). However, where the total spin - is small and the largest number of SOMOs does not exceed 14, the \(\mathbf{A}^{pq}_{ij}\) matrices + is small and the largest number of SOMOs does not exceed 14, the \(\mathbf{A}^{pq}_{ij}\) matrices can be stored in memory. - +