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mirror of https://gitlab.com/scemama/QCaml.git synced 2024-12-06 20:43:33 +01:00

Working on DIIS

This commit is contained in:
Anthony Scemama 2018-05-31 16:46:45 +02:00
parent 47864a9fb7
commit 3482e02695
15 changed files with 205 additions and 61 deletions

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@ -3,5 +3,5 @@ S .
S Nuclei
S Utils
S Basis
S HartreeFock
S SCF
B _build/**

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@ -1,17 +0,0 @@
open Lacaml.D
type guess =
| Hcore of Mat.t
type t = guess
let make ?guess:(guess=`Hcore) simulation =
let eN_ints = Lazy.force simulation.Simulation.eN_ints
and kin_ints = Lazy.force simulation.Simulation.kin_ints
in
match guess with
| `Hcore -> Hcore (Mat.add eN_ints kin_ints)

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@ -1,12 +0,0 @@
(** Guess for Hartree-Fock calculations. *)
type guess =
| Hcore of Lacaml.D.Mat.t
type t = guess
val make : ?guess:[ `Hcore ] -> Simulation.t -> t

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@ -1,6 +1,6 @@
.NOPARALLEL:
INCLUDE_DIRS=Nuclei,Utils,Basis,HartreeFock
INCLUDE_DIRS=Nuclei,Utils,Basis,SCF
LIBS=
PKGS=
OCAMLBUILD=ocamlbuild -j 0 -cflags $(ocamlcflags) -lflags $(ocamlcflags) $(ocamldocflags) -Is $(INCLUDE_DIRS) -ocamlopt $(ocamloptflags)

49
SCF/Guess.ml Normal file
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@ -0,0 +1,49 @@
open Lacaml.D
open Util
type guess =
| Hcore of Mat.t
| Huckel of Mat.t
type t = guess
module Si = Simulation
module El = Electrons
let hcore_guess simulation =
let eN_ints = Lazy.force simulation.Si.eN_ints
and kin_ints = Lazy.force simulation.Si.kin_ints
in
Mat.add eN_ints kin_ints
let huckel_guess simulation =
let c = 0.5 *. 1.75 in
let ao_num = Basis.size simulation.Si.basis in
let eN_ints = Lazy.force simulation.Si.eN_ints
and kin_ints = Lazy.force simulation.Si.kin_ints
and overlap = Lazy.force simulation.Si.overlap
and m_X = Lazy.force simulation.Si.overlap_ortho
in
let diag = Array.init (ao_num+1) (fun i -> if i=0 then 0. else
eN_ints.{i,i} +. kin_ints.{i,i})
in
let nocc =
simulation.Si.electrons.El.n_alpha
in
let m_F = (Fock.make ~density:(gemm ~alpha:2. ~transb:`T ~k:nocc m_X m_X) simulation).Fock.fock in
for j=1 to ao_num do
for i=1 to ao_num do
if (i <> j) then
m_F.{i,j} <- c *. overlap.{i,j} *. (diag.(i) +. diag.(j)) (*TODO Pseudo *)
done;
done;
m_F
let make ~guess simulation =
match guess with
| `Hcore -> Hcore (hcore_guess simulation)
| `Huckel -> Huckel (huckel_guess simulation)

13
SCF/Guess.mli Normal file
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@ -0,0 +1,13 @@
(** Guess for Hartree-Fock calculations. *)
type guess =
| Hcore of Lacaml.D.Mat.t
| Huckel of Lacaml.D.Mat.t
type t = guess
val make : guess:[ `Hcore | `Huckel ] -> Simulation.t -> t

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@ -2,7 +2,7 @@ open Util
open Lacaml.D
open Simulation
let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
let make ?guess:(guess=`Huckel) ?max_scf:(max_scf=64) ?level_shift:(level_shift=0.1)
?threshold_SCF:(threshold_SCF=1.e-6) simulation =
(* Number of occupied MOs *)
@ -21,7 +21,7 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
(* Orthogonalization matrix *)
let m_X =
Lazy.force simulation.overlap_ortho
Lazy.force simulation.overlap_ortho
in
@ -34,8 +34,16 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
and m_V = Lazy.force simulation.eN_ints
in
(* Level shift *)
let m_LS =
Array.init (Mat.dim2 m_X) (fun i ->
if i > nocc then level_shift else 0.)
|> Vec.of_array
|> Mat.of_diag
in
(* SCF iterations *)
let rec loop nSCF iterations m_C =
let rec loop nSCF iterations m_C diis =
(* Density matrix over nocc occupied MOs *)
let m_P =
@ -50,9 +58,31 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
x.Fock.fock, x.Fock.core, x.Fock.coulomb, x.Fock.exchange
in
let error_fock =
let fps =
gemm m_F (gemm m_P m_S)
and spf =
gemm m_S (gemm m_P m_F)
in
Mat.sub fps spf
in
let diis =
DIIS.append ~p:(Mat.as_vec m_F) ~e:(Mat.as_vec error_fock) diis
in
let m_F_diis =
let x =
Bigarray.genarray_of_array1 (DIIS.next diis)
in
Bigarray.reshape_2 x (Mat.dim1 m_F) (Mat.dim2 m_F)
in
(* Fock matrix in MO basis *)
let m_Fmo =
xt_o_x m_F m_X
xt_o_x m_F_diis m_C
|> Mat.add m_LS
in
(* MOs in old MO basis *)
@ -62,7 +92,7 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
(* MOs in AO basis *)
let m_C =
gemm m_X m_C'
gemm m_C m_C'
in
(* Hartree-Fock energy *)
@ -72,32 +102,28 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
in
(* Convergence criterion *)
let commutator =
let fps =
gemm m_F (gemm m_P m_S)
and spf =
gemm m_S (gemm m_P m_F)
in
Mat.sub fps spf
|> Mat.as_vec
let error =
xt_o_x error_fock m_C
|> Mat.as_vec
|> amax
|> abs_float
in
let converged =
nSCF = max_scf || (abs_float commutator) < threshold_SCF
nSCF = max_scf || error < threshold_SCF
in
let gap =
eigenvalues.{nocc+1} -. eigenvalues.{nocc};
in
Printf.printf "%d %16.10f %11.4e %10.4f\n%!" nSCF energy commutator gap;
Printf.printf "%d %16.10f %11.4e %10.4f\n%!" nSCF energy error gap;
if not converged then
loop (nSCF+1) ( (energy, commutator, gap) :: iterations) m_C
loop (nSCF+1) ( (energy, error, gap) :: iterations) m_C diis
else
let iterations =
List.rev ( (energy, commutator, gap) :: iterations )
List.rev ( (energy, error, gap) :: iterations )
|> Array.of_list
in
{ HartreeFock_type.
@ -120,6 +146,7 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
let m_H =
match guess with
| Guess.Hcore m_H -> m_H
| Guess.Huckel m_H -> m_H
in
let m_Hmo =
xt_o_x m_H m_X
@ -131,7 +158,8 @@ let make ?guess:(guess=`Hcore) ?max_scf:(max_scf=64)
gemm m_X m_C'
in
loop 1 [] m_C
let diis = DIIS.make () in
loop 1 [] m_C diis

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@ -12,7 +12,7 @@ type t = {
cartesian : bool;
}
let make ?cartesian:(cartesian=true)
let make ?cartesian:(cartesian=false)
?multiplicity:(multiplicity=1)
?charge:(charge=0)
~nuclei

60
Utils/DIIS.ml Normal file
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@ -0,0 +1,60 @@
open Lacaml.D
open Util
type t =
{
p : Vec.t list;
e : Vec.t list;
m : int;
mmax : int;
}
let make ?mmax:(mmax=15) () =
assert (mmax > 1);
{
p = [];
e = [];
m = 0 ;
mmax;
}
let append ~p ~e diis =
let update v l =
if diis.m < diis.mmax then
v :: l
else
match List.rev l with
| [] -> assert false
| _ :: rest -> v :: List.rev rest
in
{ diis with
p = update p diis.p;
e = update e diis.e;
m = min diis.mmax (diis.m+1);
}
let next diis =
let e = Mat.of_col_vecs_list diis.e
and p = Mat.of_col_vecs_list diis.p
in
let a =
let rec aux m =
let a = Mat.make (m+1) (m+1) 1. in
a.{m+1,m+1} <- 0.;
ignore @@ lacpy ~b:a (gemm ~transa:`T ~m ~n:m e e);
if sycon (lacpy a) > 1.e-10 then a
else aux (m-1)
in
aux diis.m
in
let m = Mat.dim1 a - 1 in
let c = Mat.make0 (m+1) 1 in
c.{m+1,1} <- 1.;
sysv a c;
gemm p c ~k:m
|> Mat.as_vec

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@ -29,13 +29,13 @@ Equating zero to the derivatives of {% $\mathcal{L}$ %} with respect to {% $c_i$
{% \begin{equation*}
\begin{bmatrix}
B_{11} & B_{12} & B_{13} & ... & B_{1m} & -1 \\
B_{21} & B_{22} & B_{23} & ... & B_{2m} & -1 \\
B_{31} & B_{32} & B_{33} & ... & B_{3m} & -1 \\
B_{11} & B_{12} & B_{13} & ... & B_{1m} & 1 \\
B_{21} & B_{22} & B_{23} & ... & B_{2m} & 1 \\
B_{31} & B_{32} & B_{33} & ... & B_{3m} & 1 \\
\vdots & \vdots & \vdots & \vdots & \ddots & \vdots \\
B_{m1} & B_{m2} & B_{m3} & ... & B_{mm} & -1 \\
B_{m1} & B_{m2} & B_{m3} & ... & B_{mm} & 1 \\
1 & 1 & 1 & ... & 1 & 0
\end{bmatrix} \begin{bmatrix} c_1 \\ c_2 \\ c_3 \\ \vdots \\ c_m \\ \lambda \end{bmatrix}=
\end{bmatrix} \begin{bmatrix} c_1 \\ c_2 \\ c_3 \\ \vdots \\ c_m \\ -\lambda \end{bmatrix}=
\begin{bmatrix} 0 \\ 0 \\ 0 \\ \vdots \\ 0 \\ 1 \end{bmatrix}
\end{equation*}
@ -50,10 +50,10 @@ $$ %}
type t
val make : unit -> t
(** Initialize DIIS *)
val make : ?mmax:int -> unit -> t
(** Initialize DIIS with a maximum size.*)
val append : p:Lacaml.D.Vec.t -> e:Lacaml.D.Vec.t -> t
val append : p:Lacaml.D.Vec.t -> e:Lacaml.D.Vec.t -> t -> t
(** Append a parameter vector [p] and the corresponding error vector [e]. *)
val next : t -> Lacaml.D.Vec.t

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@ -171,9 +171,8 @@ let array_product a =
let diagonalize_symm m_H =
let m_V = lacpy m_H in
let m_W = Vec.create (Mat.dim1 m_H) in
let result =
syevd ~vectors:true ~w:m_W m_V
syevd ~vectors:true m_V
in
m_V, result
@ -200,8 +199,32 @@ let canonical_ortho ?thresh:(thresh=1.e-6) ~overlap c =
gemm c u
let string_of_matrix m =
let open Lacaml.Io in
let rows = Mat.dim1 m
and cols = Mat.dim2 m
in
let rec aux accu first last =
if (first > last) then String.concat "\n" (List.rev accu)
else
let nw =
Format.asprintf "\n\n %a\n" (Lacaml.Io.pp_lfmat
~row_labels:
(Array.init rows (fun i -> Printf.sprintf "%d " (i + 1)))
~col_labels:
(Array.init (min 5 (cols-first+1)) (fun i -> Printf.sprintf "-- %d --" (i + first) ))
~print_right:false
~print_foot:false
() ) (lacpy ~ac:first ~n:(min 5 (cols-first+1)) m)
in
aux (nw :: accu) (first+5) last
in
aux [] 1 cols
let debug_matrix name a =
Format.printf "@[<2>%s =@\n@\n@[%a@]@]@\n@\n" name pp_mat a
Printf.printf "%s =\n%s\n" name (string_of_matrix a)