mirror of
https://gitlab.com/scemama/QCaml.git
synced 2024-08-30 00:03:42 +02:00
427 lines
12 KiB
OCaml
427 lines
12 KiB
OCaml
open Lacaml.D
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module Ds = DeterminantSpace
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module De = Determinant
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module Sp = Spindeterminant
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type t =
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{
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mo_basis : MOBasis.t ;
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det_space : DeterminantSpace.t ;
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ci : CI.t ;
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hf12_integrals : HF12.t ;
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eigensystem : (Mat.t * Vec.t) lazy_t;
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}
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let ci t = t.ci
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let mo_basis t = t.mo_basis
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let det_space t = t.det_space
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let mo_class t = Ds.mo_class @@ det_space t
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let eigensystem t = Lazy.force t.eigensystem
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(*
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let single_matrices hf12_integrals density =
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let nocc = Mat.dim1 density in
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let nvir = Mat.dim2 density in
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let { HF12.
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simulation ; aux_basis ;
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hf12 ; hf12_anti ;
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hf12_single ; hf12_single_anti } = hf12_integrals
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in
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let f12 = MOBasis.f12_ints aux_basis in
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let eri = MOBasis.two_e_ints aux_basis in
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let d = Mat.as_vec density in
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let v_s = Mat.create nocc nvir in
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let v_o = Mat.create nocc nvir in
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let h_o, h_s, f_o, f_s =
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Mat.create nocc nvir ,
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Mat.create nocc nvir ,
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Mat.create nocc nvir ,
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Mat.create nocc nvir ,
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in
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for a=1 to nvir do
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for m=1 to occ do
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for u=1 to nocc do
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for t=1 to nocc do
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let hmtau = ERI.get_phys eri m t a u
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and hmtua = ERI.get_phys eri m t u a
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in
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v_o.{t,u} <- hmtau;
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v_s.{t,u} <- hmtau -. hmtua;
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done
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done;
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h_o.{m,a} <- dot d_o @@ Mat.as_vec v_o;
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h_s.{m,a} <- dot d_s @@ Mat.as_vec v_s
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for u=1 to nocc do
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for t=1 to nocc do
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let fmtau = ERI.get_phys f12 m t a u
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and fmtua = ERI.get_phys f12 m t u a
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in
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v_o.{t,u} <- 0.375 *. fmtau +. 0.125 *. fmtua;
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v_s.{t,u} <- 0.25 *, (fmtau -. fmtua);
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done
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done;
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f_o.{m,a} <- dot d_o @@ Mat.as_vec v_o;
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f_s.{m,a} <- dot d_s @@ Mat.as_vec v_s
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done
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done;
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*)
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(*---
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let hf_ij_non_zero mo_basis hf12_integrals deg_a deg_b ki kj =
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let integrals = [
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let { HF12.
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simulation ; aux_basis ;
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hf12 ; hf12_anti ;
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hf12_single ; hf12_single_anti } = hf12_integrals
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in
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let kia = De.alfa ki and kib = De.beta ki in
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let kja = De.alfa kj and kjb = De.beta kj in
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let mo_a =
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Bitstring.logand (Sp.bitstring kia) (Sp.bitstring kja)
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|> Bitstring.to_list
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|> Array.of_list
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and mo_b =
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Bitstring.logand (Sp.bitstring kib) (Sp.bitstring kjb)
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|> Bitstring.to_list
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|> Array.of_list
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in
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let aux_mos =
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Util.list_range (MOBasis.size mo_basis) (MOBasis.size aux_basis)
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|> Array.of_list
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in
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let one_e _ _ _ = 0. in
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let h = MOBasis.ee_ints aux_basis in
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let two_e_h i j k l s s' =
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if s' <> s then
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ERI.get_phys h i j k l
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else
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(ERI.get_phys h i j k l) -. (ERI.get_phys h i j l k)
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in
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let f = MOBasis.f12_ints aux_basis in
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let two_e_f i j k l s s' =
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let fijkl = F12.get_phys f i j k l
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and fijlk = F12.get_phys f i j l k
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in
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if s' <> s then
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0.325 *. fijkl +. 0.125 *. fijlk
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else
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0.25 *. (fijkl -. fijlk)
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in
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(*
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let mo_of_s = function
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| Spin.Alfa -> mo_a
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| Spin.Beta -> mo_b
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in
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*)
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let two_e i j k l s s' =
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(
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if s = s' then
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hf12_anti.{i,j,k,l} -. (
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(Array.fold_left (fun accu m -> accu +. hf12_single_anti.{m,i,j,k,l}) 0. mo_a) +.
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(Array.fold_left (fun accu m -> accu +. hf12_single_anti.{m,j,i,l,k}) 0. mo_b) )
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else
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hf12.{i,j,k,l} -. (
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(Array.fold_left (fun accu m -> accu +. hf12_single.{m,i,j,k,l}) 0. mo_a) +.
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(Array.fold_left (fun accu m -> accu +. hf12_single.{m,j,i,l,k}) 0. mo_b) )
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)
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(*
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+. Array.fold_left ( fun accu a -> accu +.
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(Array.fold_left ( fun accu m -> accu +. two_e_h m i m a s s) 0. (mo_of_s s) +.
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Array.fold_left ( fun accu m -> accu +. two_e_h m i m a s s) 0. (mo_of_s @@ Spin.other s) )
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*. (two_e_f a j k l s s') ) 0. aux_mos
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*)
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in
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let three_e i j k l m n s s' s'' =
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Array.fold_left (fun accu a -> accu +. two_e_h i j l a s s' *. two_e_f a k m n s' s'') 0. aux_mos
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-. Array.fold_left (fun accu a -> accu +. two_e_h j i m a s' s *. two_e_f a k l n s s'') 0. aux_mos
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+. Array.fold_left (fun accu a -> accu +. two_e_h j k m a s' s'' *. two_e_f a i n l s'' s ) 0. aux_mos
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-. Array.fold_left (fun accu a -> accu +. two_e_h k j n a s'' s' *. two_e_f a i m l s' s ) 0. aux_mos
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+. Array.fold_left (fun accu a -> accu +. two_e_h k i n a s'' s *. two_e_f a j l m s s' ) 0. aux_mos
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-. Array.fold_left (fun accu a -> accu +. two_e_h i k l a s s'' *. two_e_f a j n m s'' s' ) 0. aux_mos
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in
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(one_e, two_e, Some three_e)
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]
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in
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CIMatrixElement.non_zero integrals deg_a deg_b ki kj
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|> List.hd
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let dressing_vector ~frozen_core hf12_integrals f12_amplitudes ci =
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if Parallel.master then
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Printf.printf "Building matrix\n%!";
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let det_space =
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ci.CI.det_space
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in
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let mo_basis =
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Ds.mo_basis det_space
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in
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let m_HF =
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let f =
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match Ds.determinants det_space with
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| Ds.Arbitrary _ -> CI.create_matrix_arbitrary
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| Ds.Spin _ -> CI.create_matrix_spin_computed ~nmax:3
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in
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f (fun deg_a deg_b ki kj ->
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hf_ij_non_zero mo_basis hf12_integrals deg_a deg_b ki kj
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) det_space
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in
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Matrix.mm (Lazy.force m_HF) (Matrix.dense_of_mat f12_amplitudes)
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--- *)
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let hf_ij_non_zero hf12_integrals deg_a deg_b ki kj =
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let integrals = [
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let { HF12.
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simulation ; aux_basis ;
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hf12 ; hf12_anti ;
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hf12_single ; hf12_single_anti } = hf12_integrals
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in
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let kia = De.alfa ki and kib = De.beta ki in
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let kja = De.alfa kj and kjb = De.beta kj in
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let mo_a =
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Bitstring.logand (Sp.bitstring kia) (Sp.bitstring kja)
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|> Bitstring.to_list
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and mo_b =
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Bitstring.logand (Sp.bitstring kib) (Sp.bitstring kjb)
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|> Bitstring.to_list
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in
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let one_e _ _ _ = 0. in
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let two_e i j k l s s' =
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if s = s' then
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hf12_anti.{i,j,k,l} -. (
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(List.fold_left (fun accu m -> accu +. hf12_single_anti.{m,i,j,k,l}) 0. mo_a) +.
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(List.fold_left (fun accu m -> accu +. hf12_single_anti.{m,j,i,l,k}) 0. mo_b)
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)
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else
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hf12.{i,j,k,l} -. (
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(List.fold_left (fun accu m -> accu +. hf12_single.{m,i,j,k,l}) 0. mo_a) +.
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(List.fold_left (fun accu m -> accu +. hf12_single.{m,j,i,l,k}) 0. mo_b)
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)
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in
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let h = MOBasis.ee_ints aux_basis in
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let two_e_h i j k l s s' =
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if s' <> s then
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ERI.get_phys h l k j i
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else
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(ERI.get_phys h l k j i) -. (ERI.get_phys h k l j i)
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in
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let f = MOBasis.f12_ints aux_basis in
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let two_e_f i j k l s s' =
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if s' <> s then
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F12.get_phys f i j k l
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else
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(F12.get_phys f i j k l) -. (F12.get_phys f i j l k)
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in
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let mo_of_s = function
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| Spin.Alfa -> mo_a
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| Spin.Beta -> mo_b
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in
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let three_e i j k l m n s s' s'' =
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List.fold_left (fun accu a -> accu +. two_e_h i j l a s s' *. two_e_f a k m n s' s'') 0. (mo_of_s s' )
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-. List.fold_left (fun accu a -> accu +. two_e_h j i m a s' s *. two_e_f a k l n s s'') 0. (mo_of_s s )
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+. List.fold_left (fun accu a -> accu +. two_e_h j k m a s' s'' *. two_e_f a i n l s'' s ) 0. (mo_of_s s'')
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-. List.fold_left (fun accu a -> accu +. two_e_h k j n a s'' s' *. two_e_f a i m l s' s ) 0. (mo_of_s s' )
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+. List.fold_left (fun accu a -> accu +. two_e_h k i n a s'' s *. two_e_f a j l m s s' ) 0. (mo_of_s s )
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-. List.fold_left (fun accu a -> accu +. two_e_h i k l a s s'' *. two_e_f a j n m s'' s' ) 0. (mo_of_s s'')
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in
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(one_e, two_e, Some three_e)
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]
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in
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CIMatrixElement.non_zero integrals deg_a deg_b ki kj
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|> List.hd
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let dressing_vector ~frozen_core hf12_integrals f12_amplitudes ci =
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if Parallel.master then
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Printf.printf "Building matrix\n%!";
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let det_space =
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ci.CI.det_space
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in
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let m_HF =
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let f =
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match Ds.determinants det_space with
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| Ds.Arbitrary _ -> CI.create_matrix_arbitrary
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| Ds.Spin _ -> CI.create_matrix_spin_computed ~nmax:3
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in
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f (fun deg_a deg_b ki kj ->
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hf_ij_non_zero hf12_integrals deg_a deg_b ki kj
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) det_space
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in
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Matrix.mm (Lazy.force m_HF) (Matrix.dense_of_mat f12_amplitudes)
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let make ~simulation ?(threshold=1.e-12) ~frozen_core ~mo_basis ~aux_basis_filename ?(state=1) () =
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let det_space =
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DeterminantSpace.fci_of_mo_basis mo_basis ~frozen_core
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in
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let ci = CI.make ~n_states:state det_space in
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let hf12_integrals =
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HF12.make ~simulation ~mo_basis ~aux_basis_filename ()
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in
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let ci_coef, ci_energy =
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let x = Lazy.force ci.eigensystem in
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Parallel.broadcast (lazy x)
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in
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let eigensystem = lazy (
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let m_H =
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Lazy.force ci.CI.m_H
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in
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let rec iteration ~state psi =
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(*
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Format.printf "%a@." DeterminantSpace.pp_det_space @@ CI.det_space ci;
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Format.printf "%a@." Matrix.pp_matrix @@ Matrix.dense_of_mat psi;
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*)
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let column_idx = iamax (Mat.to_col_vecs psi).(state-1) in
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let delta =
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(* delta_i = {% $\sum_j c_j H_{ij}$ %} *)
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dressing_vector ~frozen_core hf12_integrals psi ci
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|> Matrix.to_mat
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in
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(*
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Format.printf "%a@." Matrix.pp_matrix @@ Matrix.dense_of_mat delta;
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*)
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Printf.printf "Cmax : %e\n" psi.{column_idx,state};
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Printf.printf "Norm : %e\n" (sqrt (gemm ~transa:`T delta delta).{state,state});
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let f = 1.0 /. psi.{column_idx,state} in
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let delta_00 =
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(* Delta_00 = {% $\sum_{j \ne x} delta_j c_j / c_x$ %} *)
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f *. ( (gemm ~transa:`T delta psi).{state,state} -.
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delta.{column_idx,state} *. psi.{column_idx,state} )
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in
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Printf.printf "Delta_00 : %e %e\n" delta.{column_idx,state} delta_00;
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delta.{column_idx,state} <- delta.{column_idx,state} -. delta_00;
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let eigenvectors, eigenvalues =
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let delta = lacpy delta in
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Mat.scal f delta;
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for k=1 to state-1 do
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for i=1 to Mat.dim1 delta do
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delta.{i,k} <- delta.{i,state}
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done;
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done;
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let diagonal =
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Vec.init (Matrix.dim1 m_H) (fun i ->
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if i = column_idx then
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Matrix.get m_H i i +. delta.{column_idx,state}
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else
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Matrix.get m_H i i
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)
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in
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let matrix_prod c =
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let w =
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Matrix.mm ~transa:`T m_H c
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|> Matrix.to_mat
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in
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let c = Matrix.to_mat c in
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for k=1 to state do
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for i=1 to (Mat.dim1 w) do
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w.{i,k} <- w.{i,k} +. delta.{i,k} *. c.{column_idx, k} ;
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w.{column_idx,k} <- w.{column_idx,k} +. delta.{i,k} *. c.{i,k};
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done;
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w.{column_idx,k} <- w.{column_idx,k} -.
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delta.{column_idx,k} *. c.{column_idx,k};
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done;
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Matrix.dense_of_mat w
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in
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Parallel.broadcast (lazy (
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Davidson.make ~threshold:1.e-10 ~guess:psi ~n_states:state diagonal matrix_prod
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))
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in
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let eigenvectors =
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Conventions.rephase @@ Util.remove_epsilons eigenvectors
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in
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Vec.iter (fun energy -> Printf.printf "%g\t" energy) eigenvalues;
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print_newline ();
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let conv =
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1.0 -. abs_float ( dot
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(Mat.to_col_vecs psi).(0)
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(Mat.to_col_vecs eigenvectors).(0) )
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in
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if Parallel.master then
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Printf.printf "F12 Convergence : %e %f\n" conv (eigenvalues.{state}
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+. Simulation.nuclear_repulsion simulation);
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(*
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let cabs_singles =
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let f =
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Fock.make_rhf ~density ~ao_basis:large_ao_basis
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in
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in
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*)
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if conv > threshold then
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iteration ~state eigenvectors
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else
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let eigenvalues =
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Vec.map (fun x -> x +. ci.CI.e_shift) eigenvalues
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in
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eigenvectors, eigenvalues
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in
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iteration ~state ci_coef
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)
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in
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{ mo_basis ; det_space ; ci ; hf12_integrals ; eigensystem }
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