open Qputils open Qptypes open Core let spec = let open Command.Spec in empty +> flag "o" (optional string) ~doc:"file Name of the created EZFIO file." +> flag "b" (required string) ~doc:"string Name of basis set." +> flag "au" no_arg ~doc:"Input geometry is in atomic units." +> flag "c" (optional_with_default 0 int) ~doc:"int Total charge of the molecule. Default is 0." +> flag "d" (optional_with_default 0. float) ~doc:"float Add dummy atoms. x * (covalent radii of the atoms)" +> flag "m" (optional_with_default 1 int) ~doc:"int Spin multiplicity (2S+1) of the molecule. Default is 1." +> flag "p" (optional string) ~doc:"string Name of the pseudopotential" +> flag "cart" no_arg ~doc:" Compute AOs in the Cartesian basis set (6d, 10f, ...)" +> anon ("(xyz_file|zmt_file)" %: file ) type element = | Element of Element.t | Int_elem of (Nucl_number.t * Element.t) (** Handle dummy atoms placed on bonds *) let dummy_centers ~threshold ~molecule ~nuclei = let d = Molecule.distance_matrix molecule in let n = Array.length d in let nuclei = Array.of_list nuclei in let rec aux accu = function | (-1,_) -> accu | (i,-1) -> aux accu (i-1,i-1) | (i,j) when (i>j) -> let new_accu = let x,y = Element.covalent_radius (nuclei.(i)).Atom.element |> Positive_float.to_float, Element.covalent_radius (nuclei.(j)).Atom.element |> Positive_float.to_float in let r = ( x +. y ) *. threshold in if d.(i).(j) < r then (i,x,j,y,d.(i).(j)) :: accu else accu in aux new_accu (i,j-1) | (i,j) when (i=j) -> aux accu (i,j-1) | _ -> assert false in aux [] (n-1,n-1) |> List.map ~f:(fun (i,x,j,y,r) -> let f = x /. (x +. y) in let u = Point3d.of_tuple ~units:Units.Bohr ( nuclei.(i).Atom.coord.Point3d.x +. (nuclei.(j).Atom.coord.Point3d.x -. nuclei.(i).Atom.coord.Point3d.x) *. f, nuclei.(i).Atom.coord.Point3d.y +. (nuclei.(j).Atom.coord.Point3d.y -. nuclei.(i).Atom.coord.Point3d.y) *. f, nuclei.(i).Atom.coord.Point3d.z +. (nuclei.(j).Atom.coord.Point3d.z -. nuclei.(i).Atom.coord.Point3d.z) *. f) in Atom.{ element = Element.X ; charge = Charge.of_int 0 ; coord = u } ) (** Returns the list of available basis sets *) let list_basis () = let basis_list = Qpackage.root ^ "/install/emsl/EMSL_api.py list_basis" |> Unix.open_process_in |> In_channel.input_lines |> List.map ~f:(fun x -> match String.split x ~on:'\'' with | [] -> "" | a :: [] | _ :: a :: _ -> String.strip a ) in List.sort basis_list ~compare:String.ascending |> String.concat ~sep:"\n" (** Run the program *) let run ?o b au c d m p cart xyz_file = (* Read molecule *) let molecule = if au then (Molecule.of_file xyz_file ~charge:(Charge.of_int c) ~multiplicity:(Multiplicity.of_int m) ~units:Units.Bohr) else (Molecule.of_file xyz_file ~charge:(Charge.of_int c) ~multiplicity:(Multiplicity.of_int m) ) in let dummy = dummy_centers ~threshold:d ~molecule ~nuclei:molecule.Molecule.nuclei in let nuclei = molecule.Molecule.nuclei @ dummy in (********** Basis set **********) let basis_table = Hashtbl.Poly.create () in (* Open basis set channels *) let basis_channel element = let key = match element with | Element e -> Element.to_string e | Int_elem (i,e) -> Printf.sprintf "%d,%s" (Nucl_number.to_int i) (Element.to_string e) in match Hashtbl.find basis_table key with | Some in_channel -> in_channel | None -> raise Caml.Not_found in let temp_filename = Filename.temp_file "qp_create_" ".basis" in let () = Sys.remove temp_filename in let fetch_channel basis = let command = Qpackage.root ^ "/scripts/get_basis.sh \"" ^ temp_filename ^ "." ^ basis ^ "\" \"" ^ basis ^"\"" in let long_basis = Qpackage.root ^ "/data/basis/" ^ basis in match Sys.is_file basis, Sys.is_file long_basis with | `Yes, _ -> In_channel.create basis | `No , `Yes -> In_channel.create long_basis | _ -> begin let filename = Unix.open_process_in command |> In_channel.input_all |> String.strip in let new_channel = In_channel.create filename in Unix.unlink filename; new_channel end in let rec build_basis = function | [] -> () | elem_and_basis_name :: rest -> begin match (String.lsplit2 ~on:':' elem_and_basis_name) with | None -> (* Principal basis *) begin let basis = elem_and_basis_name in let new_channel = fetch_channel basis in List.iter nuclei ~f:(fun elem-> let key = Element.to_string elem.Atom.element in match Hashtbl.add basis_table ~key:key ~data:new_channel with | `Ok -> () | `Duplicate -> () ) end | Some (key, basis) -> (*Aux basis *) begin let elem = try Element (Element.of_string key) with Element.ElementError _ -> let result = match (String.split ~on:',' key) with | i :: k :: [] -> (Nucl_number.of_int @@ int_of_string i, Element.of_string k) | _ -> failwith "Expected format is int,Element:basis" in Int_elem result and basis = String.lowercase basis in let key = match elem with | Element e -> Element.to_string e | Int_elem (i,e) -> Printf.sprintf "%d,%s" (Nucl_number.to_int i) (Element.to_string e) in let new_channel = fetch_channel basis in begin match Hashtbl.add basis_table ~key:key ~data:new_channel with | `Ok -> () | `Duplicate -> let e = match elem with | Element e -> e | Int_elem (_,e) -> e in failwith ("Duplicate definition of basis for "^(Element.to_long_string e)) end end end; build_basis rest in String.split ~on:'|' b |> List.rev_map ~f:String.strip |> build_basis; (*************** Pseudopotential ***************) let pseudo_table = Hashtbl.Poly.create () in (* Open pseudo channels *) let pseudo_channel element = let key = Element.to_string element in Hashtbl.find pseudo_table key in let temp_filename = Filename.temp_file "qp_create_" ".pseudo" in let () = Sys.remove temp_filename in let fetch_channel pseudo = let long_pseudo = Qpackage.root ^ "/data/pseudo/" ^ pseudo in match Sys.is_file pseudo, Sys.is_file long_pseudo with | `Yes, _ -> In_channel.create pseudo | `No , `Yes -> In_channel.create long_pseudo | _ -> failwith ("Pseudo file "^pseudo^" not found.") in let rec build_pseudo = function | [] -> () | elem_and_pseudo_name :: rest -> begin match (String.lsplit2 ~on:':' elem_and_pseudo_name) with | None -> (* Principal pseudo *) begin let pseudo = elem_and_pseudo_name in let new_channel = fetch_channel pseudo in List.iter nuclei ~f:(fun elem-> let key = Element.to_string elem.Atom.element in match Hashtbl.add pseudo_table ~key:key ~data:new_channel with | `Ok -> () | `Duplicate -> () ) end | Some (key, pseudo) -> (*Aux pseudo *) begin let elem = Element.of_string key and pseudo = String.lowercase pseudo in let key = Element.to_string elem in let new_channel = fetch_channel pseudo in begin match Hashtbl.add pseudo_table ~key:key ~data:new_channel with | `Ok -> () | `Duplicate -> failwith ("Duplicate definition of pseudo for "^(Element.to_long_string elem)) end end end; build_pseudo rest in let () = match p with | None -> () | Some p -> String.split ~on:'|' p |> List.rev_map ~f:String.strip |> build_pseudo in (* Build EZFIO File name *) let ezfio_file = match o with | Some x -> x | None -> begin match String.rsplit2 ~on:'.' xyz_file with | Some (x,"xyz") | Some (x,"zmt") -> x^".ezfio" | _ -> xyz_file^".ezfio" end in if Sys.file_exists_exn ezfio_file then failwith (ezfio_file^" already exists"); let write_file () = (* Create EZFIO *) Ezfio.set_file ezfio_file; (* Write Pseudo *) let pseudo = List.map nuclei ~f:(fun x -> match pseudo_channel x.Atom.element with | Some channel -> Pseudo.read_element channel x.Atom.element | None -> Pseudo.empty x.Atom.element ) in let molecule = let n_elec_to_remove = List.fold pseudo ~init:0 ~f:(fun accu x -> accu + (Positive_int.to_int x.Pseudo.n_elec)) in { Molecule.elec_alpha = (Elec_alpha_number.to_int molecule.Molecule.elec_alpha) - n_elec_to_remove/2 |> Elec_alpha_number.of_int; Molecule.elec_beta = (Elec_beta_number.to_int molecule.Molecule.elec_beta) - (n_elec_to_remove - n_elec_to_remove/2) |> Elec_beta_number.of_int; Molecule.nuclei = let charges = List.map pseudo ~f:(fun x -> Positive_int.to_int x.Pseudo.n_elec |> Float.of_int) |> Array.of_list in List.mapi molecule.Molecule.nuclei ~f:(fun i x -> { x with Atom.charge = (Charge.to_float x.Atom.charge) -. charges.(i) |> Charge.of_float } ) } in let nuclei = molecule.Molecule.nuclei @ dummy in (* Write Electrons *) Ezfio.set_electrons_elec_alpha_num ( Elec_alpha_number.to_int molecule.Molecule.elec_alpha ) ; Ezfio.set_electrons_elec_beta_num ( Elec_beta_number.to_int molecule.Molecule.elec_beta ) ; (* Write Nuclei *) let labels = List.map ~f:(fun x->Element.to_string x.Atom.element) nuclei and charges = List.map ~f:(fun x-> Atom.(Charge.to_float x.charge)) nuclei and coords = (List.map ~f:(fun x-> x.Atom.coord.Point3d.x) nuclei) @ (List.map ~f:(fun x-> x.Atom.coord.Point3d.y) nuclei) @ (List.map ~f:(fun x-> x.Atom.coord.Point3d.z) nuclei) in let nucl_num = (List.length labels) in Ezfio.set_nuclei_nucl_num nucl_num ; Ezfio.set_nuclei_nucl_label (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| nucl_num |] ~data:labels); Ezfio.set_nuclei_nucl_charge (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| nucl_num |] ~data:charges); Ezfio.set_nuclei_nucl_coord (Ezfio.ezfio_array_of_list ~rank:2 ~dim:[| nucl_num ; 3 |] ~data:coords); (* Write pseudopotential *) let () = match p with | None -> Ezfio.set_pseudo_do_pseudo false | _ -> Ezfio.set_pseudo_do_pseudo true in let klocmax = List.fold pseudo ~init:0 ~f:(fun accu x -> let x = List.length x.Pseudo.local in if (x > accu) then x else accu ) and lmax = List.fold pseudo ~init:0 ~f:(fun accu x -> let x = List.fold x.Pseudo.non_local ~init:0 ~f:(fun accu (x,_) -> let x = Positive_int.to_int x.Pseudo.GaussianPrimitive_non_local.proj in if (x > accu) then x else accu ) in if (x > accu) then x else accu ) in let kmax = Array.init (lmax+1) ~f:(fun i-> List.map pseudo ~f:(fun x -> List.filter x.Pseudo.non_local ~f:(fun (y,_) -> (Positive_int.to_int y.Pseudo.GaussianPrimitive_non_local.proj) = i) |> List.length ) |> List.fold ~init:0 ~f:(fun accu x -> if accu > x then accu else x) ) |> Array.fold ~init:0 ~f:(fun accu i -> if i > accu then i else accu) in let () = Ezfio.set_pseudo_pseudo_klocmax klocmax; Ezfio.set_pseudo_pseudo_kmax kmax; Ezfio.set_pseudo_pseudo_lmax lmax; let tmp_array_v_k, tmp_array_dz_k, tmp_array_n_k = Array.make_matrix ~dimx:klocmax ~dimy:nucl_num 0. , Array.make_matrix ~dimx:klocmax ~dimy:nucl_num 0. , Array.make_matrix ~dimx:klocmax ~dimy:nucl_num 0 in List.iteri pseudo ~f:(fun j x -> List.iteri x.Pseudo.local ~f:(fun i (y,c) -> tmp_array_v_k.(i).(j) <- AO_coef.to_float c; let y, z = AO_expo.to_float y.Pseudo.GaussianPrimitive_local.expo, R_power.to_int y.Pseudo.GaussianPrimitive_local.r_power in tmp_array_dz_k.(i).(j) <- y; tmp_array_n_k.(i).(j) <- z; ) ); let concat_2d tmp_array = let data = Array.map tmp_array ~f:Array.to_list |> Array.to_list |> List.concat in Ezfio.ezfio_array_of_list ~rank:2 ~dim:[|nucl_num ; klocmax|] ~data in concat_2d tmp_array_v_k |> Ezfio.set_pseudo_pseudo_v_k ; concat_2d tmp_array_dz_k |> Ezfio.set_pseudo_pseudo_dz_k; concat_2d tmp_array_n_k |> Ezfio.set_pseudo_pseudo_n_k; let tmp_array_v_kl, tmp_array_dz_kl, tmp_array_n_kl = Array.init (lmax+1) ~f:(fun _ -> (Array.make_matrix ~dimx:kmax ~dimy:nucl_num 0. )), Array.init (lmax+1) ~f:(fun _ -> (Array.make_matrix ~dimx:kmax ~dimy:nucl_num 0. )), Array.init (lmax+1) ~f:(fun _ -> (Array.make_matrix ~dimx:kmax ~dimy:nucl_num 0 )) in List.iteri pseudo ~f:(fun j x -> let last_idx = Array.create ~len:(lmax+1) 0 in List.iter x.Pseudo.non_local ~f:(fun (y,c) -> let k, y, z = Positive_int.to_int y.Pseudo.GaussianPrimitive_non_local.proj, AO_expo.to_float y.Pseudo.GaussianPrimitive_non_local.expo, R_power.to_int y.Pseudo.GaussianPrimitive_non_local.r_power in let i = last_idx.(k) in tmp_array_v_kl.(k).(i).(j) <- AO_coef.to_float c; tmp_array_dz_kl.(k).(i).(j) <- y; tmp_array_n_kl.(k).(i).(j) <- z; last_idx.(k) <- i+1; ) ); let concat_3d tmp_array = let data = Array.map tmp_array ~f:(fun x -> Array.map x ~f:Array.to_list |> Array.to_list |> List.concat) |> Array.to_list |> List.concat in Ezfio.ezfio_array_of_list ~rank:3 ~dim:[|nucl_num ; kmax ; lmax+1|] ~data in concat_3d tmp_array_v_kl |> Ezfio.set_pseudo_pseudo_v_kl ; concat_3d tmp_array_dz_kl |> Ezfio.set_pseudo_pseudo_dz_kl ; concat_3d tmp_array_n_kl |> Ezfio.set_pseudo_pseudo_n_kl ; in (* Write Basis set *) let basis = let nmax = Nucl_number.get_max () in let rec do_work (accu:(Atom.t*Nucl_number.t) list) (n:int) = function | [] -> accu | e::tail -> let new_accu = (e,(Nucl_number.of_int ~max:nmax n))::accu in do_work new_accu (n+1) tail in let result = do_work [] 1 nuclei |> List.rev |> List.map ~f:(fun (x,i) -> try let e = match x.Atom.element with | Element.X -> Element.H | e -> e in let key = Int_elem (i,x.Atom.element) in try Basis.read_element (basis_channel key) i e with Caml.Not_found -> let key = Element x.Atom.element in try Basis.read_element (basis_channel key) i e with Caml.Not_found -> failwith (Printf.sprintf "Basis not found for atom %d (%s)" (Nucl_number.to_int i) (Element.to_string x.Atom.element) ) with | End_of_file -> failwith ("Element "^(Element.to_string x.Atom.element)^" not found in basis set.") ) |> List.concat in (* close all in_channels *) result in let long_basis = Long_basis.of_basis basis in let ao_num = List.length long_basis in Ezfio.set_ao_basis_ao_num ao_num; Ezfio.set_ao_basis_ao_basis b; let ao_prim_num = List.map long_basis ~f:(fun (_,g,_) -> List.length g.Gto.lc) and ao_nucl = List.map long_basis ~f:(fun (_,_,n) -> Nucl_number.to_int n) and ao_power= let l = List.map long_basis ~f:(fun (x,_,_) -> x) in (List.map l ~f:(fun t -> Positive_int.to_int Symmetry.Xyz.(t.x)) )@ (List.map l ~f:(fun t -> Positive_int.to_int Symmetry.Xyz.(t.y)) )@ (List.map l ~f:(fun t -> Positive_int.to_int Symmetry.Xyz.(t.z)) ) in let ao_prim_num_max = List.fold ~init:0 ~f:(fun s x -> if x > s then x else s) ao_prim_num in let gtos = List.map long_basis ~f:(fun (_,x,_) -> x) in let create_expo_coef ec = let coefs = begin match ec with | `Coefs -> List.map gtos ~f:(fun x-> List.map x.Gto.lc ~f:(fun (_,coef) -> AO_coef.to_float coef) ) | `Expos -> List.map gtos ~f:(fun x-> List.map x.Gto.lc ~f:(fun (prim,_) -> AO_expo.to_float prim.GaussianPrimitive.expo) ) end in let rec get_n n accu = function | [] -> List.rev accu | h::tail -> let y = begin match List.nth h n with | Some x -> x | None -> 0. end in get_n n (y::accu) tail in let rec build accu = function | n when n=ao_prim_num_max -> accu | n -> build ( accu @ (get_n n [] coefs) ) (n+1) in build [] 0 in let ao_coef = create_expo_coef `Coefs and ao_expo = create_expo_coef `Expos in let () = Ezfio.set_ao_basis_ao_prim_num (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| ao_num |] ~data:ao_prim_num) ; Ezfio.set_ao_basis_ao_nucl(Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| ao_num |] ~data:ao_nucl) ; Ezfio.set_ao_basis_ao_power(Ezfio.ezfio_array_of_list ~rank:2 ~dim:[| ao_num ; 3 |] ~data:ao_power) ; Ezfio.set_ao_basis_ao_coef(Ezfio.ezfio_array_of_list ~rank:2 ~dim:[| ao_num ; ao_prim_num_max |] ~data:ao_coef) ; Ezfio.set_ao_basis_ao_expo(Ezfio.ezfio_array_of_list ~rank:2 ~dim:[| ao_num ; ao_prim_num_max |] ~data:ao_expo) ; Ezfio.set_ao_basis_ao_cartesian(cart); in match Input.Ao_basis.read () with | None -> failwith "Error in basis" | Some x -> Input.Ao_basis.write x in let () = try write_file () with | ex -> begin begin match Sys.is_directory ezfio_file with | `Yes -> rmdir ezfio_file | _ -> () end; raise ex; end in () let command = Command.basic_spec ~summary: "Quantum Package command" ~readme:(fun () -> " === Available basis sets === " ^ (list_basis ()) ^ " ============================ Creates an EZFIO directory from a standard xyz file or from a z-matrix file in Gaussian format. The basis set is defined as a single string if all the atoms are taken from the same basis set, otherwise specific elements can be defined as follows: -b \"cc-pcvdz | H:cc-pvdz | C:6-31g\" -b \"cc-pvtz | 1,H:sto-3g | 3,H:6-31g\" If a file with the same name as the basis set exists, this file will be read. Otherwise, the basis set is obtained from the database. " ) spec (fun o b au c d m p cart xyz_file () -> run ?o b au c d m p cart xyz_file ) let () = Command.run command