Added Hartree-Fock guess with projection

This commit is contained in:
Anthony Scemama 2019-03-04 19:01:54 +01:00
parent 53cdb6f528
commit b72a1e251e
13 changed files with 154 additions and 37 deletions

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@ -7,8 +7,8 @@ type t =
overlap : Overlap.t lazy_t; overlap : Overlap.t lazy_t;
ortho : Orthonormalization.t lazy_t; ortho : Orthonormalization.t lazy_t;
eN_ints : NucInt.t lazy_t; eN_ints : NucInt.t lazy_t;
ee_ints : ERI.t lazy_t;
kin_ints : KinInt.t lazy_t; kin_ints : KinInt.t lazy_t;
ee_ints : ERI.t lazy_t;
cartesian : bool; cartesian : bool;
} }
@ -16,8 +16,8 @@ let basis t = t.basis
let overlap t = Lazy.force t.overlap let overlap t = Lazy.force t.overlap
let ortho t = Lazy.force t.ortho let ortho t = Lazy.force t.ortho
let eN_ints t = Lazy.force t.eN_ints let eN_ints t = Lazy.force t.eN_ints
let ee_ints t = Lazy.force t.ee_ints
let kin_ints t = Lazy.force t.kin_ints let kin_ints t = Lazy.force t.kin_ints
let ee_ints t = Lazy.force t.ee_ints
let cartesian t = t.cartesian let cartesian t = t.cartesian

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@ -161,6 +161,8 @@ let of_basis basis =
Mat.detri result; Mat.detri result;
result result
let of_basis_pair first_basis second_basis =
failwith "Not implemented"
(** Write all kinetic integrals to a file *) (** Write all kinetic integrals to a file *)
let to_file ~filename kinetic = let to_file ~filename kinetic =

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@ -7,6 +7,9 @@ type t
val of_basis : Basis.t -> t val of_basis : Basis.t -> t
(** Build from a {!Basis.t}. *) (** Build from a {!Basis.t}. *)
val of_basis_pair : Basis.t -> Basis.t -> t
(** Build from a pair of {!Basis.t}. *)
val to_file : filename:string -> t -> unit val to_file : filename:string -> t -> unit
(** Write the integrals in a file. *) (** Write the integrals in a file. *)

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@ -114,3 +114,6 @@ let to_file ~filename eni_array =
let of_basis basis = let of_basis basis =
invalid_arg "of_basis_nuclei should be called for NucInt" invalid_arg "of_basis_nuclei should be called for NucInt"
let of_basis_pair basis =
failwith "Not implemented"

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@ -130,6 +130,50 @@ let of_basis basis =
result result
(** Create mixed overlap matrix *)
let of_basis_pair first_basis second_basis =
let to_powers x =
let open Zkey in
match to_powers x with
| Three x -> x
| _ -> assert false
in
let n = Bs.size first_basis
and m = Bs.size second_basis
and first = Bs.contracted_shells first_basis
and second = Bs.contracted_shells second_basis
in
let result = Mat.create n m in
for j=0 to (Array.length second) - 1 do
for i=0 to (Array.length first) - 1 do
(* Compute all the integrals of the class *)
let cls =
contracted_class first.(i) second.(j)
in
Array.iteri (fun j_c powers_j ->
let j_c = Cs.index second.(j) + j_c + 1 in
let xj = to_powers powers_j in
Array.iteri (fun i_c powers_i ->
let i_c = Cs.index first.(i) + i_c + 1 in
let xi = to_powers powers_i in
let key =
Zkey.of_powers_six xi xj
in
let value =
try Zmap.find cls key
with Not_found -> 0.
in
result.{i_c,j_c} <- value;
) (Am.zkey_array (Singlet (Cs.ang_mom first.(i))))
) (Am.zkey_array (Singlet (Cs.ang_mom second.(j))))
done;
done;
result
(** Write all overlap integrals to a file *) (** Write all overlap integrals to a file *)
let to_file ~filename overlap = let to_file ~filename overlap =

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@ -8,7 +8,7 @@ module HF = HartreeFock
module Si = Simulation module Si = Simulation
type mo_type = type mo_type =
| RHF | ROHF | UHF | CASSCF | RHF | ROHF | UHF | CASSCF | Projected
| Natural of string | Natural of string
| Localized of string | Localized of string
@ -200,6 +200,45 @@ let of_hartree_fock hf =
make ~simulation ~mo_type ~mo_occupation ~mo_coef () make ~simulation ~mo_type ~mo_occupation ~mo_coef ()
let of_mo_basis simulation other =
let mo_coef =
let basis = Simulation.ao_basis simulation in
let basis_other = ao_basis other in
let m_S =
Overlap.(matrix @@ of_basis_pair
(AOBasis.basis basis)
(AOBasis.basis basis_other) )
in
let m_X = AOBasis.ortho basis in
(* Project other vectors in the current basis *)
let m_C =
gemm m_S @@ mo_coef other
in
(* Append dummy vectors to the input vectors *)
let result =
let vecs = Mat.to_col_vecs m_X in
Array.iteri (fun i v -> if (i < Array.length vecs) then vecs.(i) <- v)
(Mat.to_col_vecs m_C) ;
Mat.of_col_vecs vecs
in
(* Gram-Schmidt Orthonormalization *)
gemm m_X @@ (Util.qr_ortho @@ gemm ~transa:`T m_X result)
in
let mo_occupation =
let occ = mo_occupation other in
Vec.init (Mat.dim2 mo_coef) (fun i ->
if (i <= Vec.dim occ) then occ.{i}
else 0.)
in
make ~simulation ~mo_type:Projected ~mo_occupation ~mo_coef ()
let pp_mo ?(start=1) ?finish ppf t = let pp_mo ?(start=1) ?finish ppf t =
let open Lacaml.Io in let open Lacaml.Io in

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@ -7,7 +7,7 @@
open Lacaml.D open Lacaml.D
type mo_type = type mo_type =
| RHF | ROHF | UHF | CASSCF | RHF | ROHF | UHF | CASSCF | Projected
| Natural of string | Natural of string
| Localized of string | Localized of string
@ -51,7 +51,7 @@ val size : t -> int
(** {1 Creators} *) (** {1 Creators} *)
val make : simulation:Simulation.t -> val make : simulation:Simulation.t ->
mo_type:mo_type -> mo_type:mo_type ->
mo_occupation:Vec.t -> mo_occupation:Vec.t ->
mo_coef:Mat.t -> mo_coef:Mat.t ->
@ -61,6 +61,8 @@ val make : simulation:Simulation.t ->
val of_hartree_fock : HartreeFock.t -> t val of_hartree_fock : HartreeFock.t -> t
(** Build MOs from a Restricted Hartree-Fock calculation. *) (** Build MOs from a Restricted Hartree-Fock calculation. *)
val of_mo_basis : Simulation.t -> t -> t
(** Project the MOs of the other basis on the current one. *)
(** {1 Printers} *) (** {1 Printers} *)

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@ -1,6 +1,6 @@
.NOPARALLEL: .NOPARALLEL:
INCLUDE_DIRS=Parallel,Nuclei,Utils,Basis,SCF,MOBasis,CI INCLUDE_DIRS=Parallel,Nuclei,Utils,Basis,SCF,MOBasis,CI,F12
LIBS= LIBS=
PKGS= PKGS=
OCAMLBUILD=ocamlbuild -j 0 -cflags $(ocamlcflags) -lflags $(ocamllflags) $(ocamldocflags) -Is $(INCLUDE_DIRS) -ocamlopt $(ocamloptflags) $(mpi) OCAMLBUILD=ocamlbuild -j 0 -cflags $(ocamlcflags) -lflags $(ocamllflags) $(ocamldocflags) -Is $(INCLUDE_DIRS) -ocamlopt $(ocamloptflags) $(mpi)

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@ -4,6 +4,7 @@ open Util
type guess = type guess =
| Hcore of Mat.t | Hcore of Mat.t
| Huckel of Mat.t | Huckel of Mat.t
| Matrix of Mat.t
type t = guess type t = guess
@ -49,8 +50,7 @@ let make ?(nocc=0) ~guess ao_basis =
match guess with match guess with
| `Hcore -> Hcore (hcore_guess ao_basis) | `Hcore -> Hcore (hcore_guess ao_basis)
| `Huckel -> Huckel (huckel_guess ao_basis nocc) | `Huckel -> Huckel (huckel_guess ao_basis nocc)
| `Matrix m -> Matrix m

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@ -1,13 +1,16 @@
open Lacaml.D
(** Guess for Hartree-Fock calculations. *) (** Guess for Hartree-Fock calculations. *)
type guess = type guess =
| Hcore of Lacaml.D.Mat.t | Hcore of Mat.t (* Core Hamiltonian Matrix *)
| Huckel of Lacaml.D.Mat.t | Huckel of Mat.t (* Huckel Hamiltonian Matrix *)
| Matrix of Mat.t (* Guess Eigenvectors *)
type t = guess type t = guess
val make : ?nocc:int -> guess:[ `Hcore | `Huckel ] -> AOBasis.t -> t val make : ?nocc:int -> guess:[ `Hcore | `Huckel | `Matrix of Mat.t ] -> AOBasis.t -> t
(** {2 Tests} *) (** {2 Tests} *)

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@ -211,10 +211,6 @@ let make
Si.ao_basis simulation Si.ao_basis simulation
in in
(* Initial guess *)
let guess =
Guess.make ~nocc ~guess ao_basis
in
(* Orthogonalization matrix *) (* Orthogonalization matrix *)
let m_X = let m_X =
@ -236,17 +232,21 @@ let make
in in
(* Guess coefficients *) (* Guess coefficients *)
let m_C = let guess =
let m_H = Guess.make ~nocc ~guess ao_basis
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 in
let m_C', _ = diagonalize_symm m_Hmo in
gemm m_X m_C'
in in
let m_C =
let c_of_h m_H =
let m_Hmo = xt_o_x m_H m_X in
let m_C', _ = diagonalize_symm m_Hmo in
gemm m_X m_C'
in
match guess with
| Guess.Hcore m_H -> c_of_h m_H
| Guess.Huckel m_H -> c_of_h m_H
| Guess.Matrix m_C -> m_C
in
(* A single SCF iteration *) (* A single SCF iteration *)
let scf_iteration_rhf data = let scf_iteration_rhf data =

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@ -57,9 +57,10 @@ val empty: hartree_fock_data
val make : val make :
?kind:hartree_fock_kind -> ?kind:hartree_fock_kind ->
?guess:[ `Hcore | `Huckel ] -> ?guess:[ `Hcore | `Huckel | `Matrix of Mat.t ] ->
?max_scf:int -> ?max_scf:int ->
?level_shift:float -> ?threshold_SCF:float -> Simulation.t -> t ?level_shift:float -> ?threshold_SCF:float ->
Simulation.t -> t
(** {1 Printers} *) (** {1 Printers} *)

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@ -1,3 +1,5 @@
open Lacaml.D
let () = let () =
let open Command_line in let open Command_line in
begin begin
@ -19,10 +21,18 @@ let () =
{ short='c' ; long="charge" ; opt=Optional; { short='c' ; long="charge" ; opt=Optional;
arg=With_arg "<int>"; arg=With_arg "<int>";
doc="Total charge of the molecule. Default is 0"; } ; doc="Total charge of the molecule. Default is 0"; } ;
{ short='g' ; long="guess" ; opt=Optional;
arg=With_arg "<string>";
doc="Guess with another basis set."; } ;
] ]
end; end;
(* Handle options *) let ppf =
if Parallel.master then Format.std_formatter
else Printing.ppf_dev_null
in
let basis_file = Util.of_some @@ Command_line.get "basis" in let basis_file = Util.of_some @@ Command_line.get "basis" in
let nuclei_file = Util.of_some @@ Command_line.get "xyz" in let nuclei_file = Util.of_some @@ Command_line.get "xyz" in
@ -39,20 +49,30 @@ let () =
| None -> 1 | None -> 1
in in
let s = let s = Simulation.of_filenames
Simulation.of_filenames ~charge ~multiplicity ~nuclei:nuclei_file basis_file ~charge ~multiplicity ~nuclei:nuclei_file basis_file in
let guess =
match Command_line.get "guess" with
| None -> `Huckel
| Some filename ->
let s_guess = Simulation.of_filenames
~charge ~multiplicity ~nuclei:nuclei_file filename in
let hf = HartreeFock.make s_guess in
Format.fprintf ppf "@[%a@]@." HartreeFock.pp_hf hf;
let guess_mos =
MOBasis.of_hartree_fock hf
|> MOBasis.of_mo_basis s
in
`Matrix (MOBasis.mo_coef guess_mos)
in in
let hf = let hf = HartreeFock.make ~guess s in
HartreeFock.make s
in
let ppf = Format.fprintf ppf "@[%a@]@." HartreeFock.pp_hf hf
if Parallel.master then Format.std_formatter (*
else Printing.ppf_dev_null
in
Format.fprintf ppf "@[%a@]@." HartreeFock.pp_hf hf;
let mos = MOBasis.of_hartree_fock hf in let mos = MOBasis.of_hartree_fock hf in
Format.fprintf ppf "@[%a@]@." (fun ppf x -> MOBasis.pp_mo ppf x) mos Format.fprintf ppf "@[%a@]@." (fun ppf x -> MOBasis.pp_mo ppf x) mos
*)