QCaml/examples/ex_fci.org

#+TITLE: Full-CI

#+PROPERTY: header-args :tangle ex_fci.ml :comments link :exports code 


In this example, we write a program that makes a valence Full CI calculation with
Hartree-Fock orbitals. The molecule is read in =xyz= format and a Gaussian
atomic basis set in GAMESS format. 

* Header 

#+BEGIN_SRC ocaml
open Qcaml
open Common
open Linear_algebra

let () =
#+END_SRC


* Command-line arguments

  We use the =Command_line= module to define the following possible
  arguments:
  - =-b --basis=   : The name of the file containing the basis set
  - =-x --xyz=     : The name of the file containing the atomic coordinates
  - =-c --charge=  : The charge of the molecule
  - =-m --multiplicity= : The spin multiplicity

** Definition

   #+BEGIN_SRC ocaml
let open Command_line in
begin
  set_header_doc (Sys.argv.(0));
  set_description_doc "Computes the one- and two-electron hartree_fock on the Gaussian atomic basis set.";
  set_specs
    [ { short='b' ; long="basis" ; opt=Mandatory;
	arg=With_arg "<string>";
	doc="Name of the file containing the basis set"; } ;
      
      { short='x' ; long="xyz" ; opt=Mandatory;
	arg=With_arg "<string>";
	doc="Name of the file containing the nuclear coordinates in xyz format"; } ;

      { short='m' ; long="multiplicity" ; opt=Optional;
        arg=With_arg "<int>";
        doc="Spin multiplicity (2S+1). Default is singlet"; } ;
      
      { short='c' ; long="charge" ; opt=Optional;
        arg=With_arg "<int>";
        doc="Total charge of the molecule. Specify negative charges with 'm' instead of the minus sign, for example m1 instead of -1. Default is 0"; } ;
      
    ]
end;
   #+END_SRC


** Interpretation

   #+BEGIN_SRC ocaml
let basis_file  = Util.of_some @@ Command_line.get "basis" in
let nuclei_file = Util.of_some @@ Command_line.get "xyz" in

let charge =
  match Command_line.get "charge" with
  | Some x -> ( if x.[0] = 'm' then
                  ~- (int_of_string (String.sub x 1 (String.length x - 1)))
                else
                  int_of_string x )
  | None   -> 0
in
    
let multiplicity =
  match Command_line.get "multiplicity" with
  | Some x -> int_of_string x
  | None -> 1
in
   #+END_SRC

* Computation

  We first read the =xyz= file to create a molecule:

  #+BEGIN_SRC ocaml
let nuclei =
  Particles.Nuclei.of_xyz_file nuclei_file
in
  #+END_SRC

  Then we create a Gaussian AO basis using the atomic coordinates:
  #+BEGIN_SRC ocaml
let ao_basis =
  Ao.Basis.of_nuclei_and_basis_filename ~nuclei basis_file
in
  #+END_SRC

  We create a simulation from the nuclei and the basis set:
  #+BEGIN_SRC ocaml
let simulation =
  Simulation.make ~multiplicity ~charge ~nuclei ao_basis
in
  #+END_SRC

  and we make the Hartree-Fock computation:
  #+BEGIN_SRC ocaml
let hf =
  Mo.Hartree_fock.make ~guess:`Huckel simulation
in
  #+END_SRC

  We define the FCI determinant space:
  #+BEGIN_SRC ocaml
let mo_basis =
  Mo.Basis.of_hartree_fock hf
in

let frozen_core =
  Mo.Frozen_core.(make Large nuclei)
in

let det_space =
  Ci.Determinant_space.fci_of_mo_basis ~frozen_core mo_basis
in
  #+END_SRC

  And we run the FCI calculation:
  #+BEGIN_SRC ocaml
let ci =
  Ci.make ~det_space simulation
in
  #+END_SRC

* Output

  We print the FCI energy: 
  #+BEGIN_SRC ocaml
Format.printf "@[HF  energy : %f@]\n" (Mo.Hartree_fock.energy hf) ;
Format.printf "@[FCI energy : %a@]\n" Vector.pp (Ci.eigenvalues ci)
  #+END_SRC