open Qputils open Qptypes open Sexplib.Std 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 (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 } ) (** 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.create 63 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 Hashtbl.find basis_table key in let temp_filename = Filename.temp_file "qp_create_" ".basis" in let () = Sys.remove temp_filename in let fetch_channel basis = let long_basis = Qpackage.root ^ "/data/basis/" ^ basis in match Sys.file_exists basis, Sys.file_exists long_basis with | true , _ -> open_in basis | false, true -> open_in long_basis | _ -> failwith ("Basis "^basis^" not found") in let rec build_basis = function | [] -> () | elem_and_basis_name :: rest -> begin match (String_ext.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 (fun elem-> let key = Element.to_string elem.Atom.element in Hashtbl.add basis_table key new_channel ) nuclei end | Some (key, basis) -> (*Aux basis *) begin let elem = try Element (Element.of_string key) with Element.ElementError _ -> let result = match (String_ext.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_ascii 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 Hashtbl.add basis_table key new_channel end end; build_basis rest in String_ext.split ~on:'|' b |> List.rev_map String.trim |> build_basis; (*************** Pseudopotential ***************) let pseudo_table = Hashtbl.create 63 in (* Open pseudo channels *) let pseudo_channel element = let key = Element.to_string element in Hashtbl.find_opt 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.file_exists pseudo, Sys.file_exists long_pseudo with | true , _ -> open_in pseudo | false, true-> open_in long_pseudo | _ -> failwith ("Pseudo file "^pseudo^" not found.") in let rec build_pseudo = function | [] -> () | elem_and_pseudo_name :: rest -> begin match (String_ext.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 (fun elem-> let key = Element.to_string elem.Atom.element in Hashtbl.add pseudo_table key new_channel ) nuclei end | Some (key, pseudo) -> (*Aux pseudo *) begin let elem = Element.of_string key and pseudo = String.lowercase_ascii pseudo in let key = Element.to_string elem in let new_channel = fetch_channel pseudo in Hashtbl.add pseudo_table key new_channel end end; build_pseudo rest in let () = match p with | None -> () | Some p -> String_ext.split ~on:'|' p |> List.rev_map String.trim |> build_pseudo in (* Build EZFIO File name *) let ezfio_file = match o with | Some x -> x | None -> begin match String_ext.rsplit2 ~on:'.' xyz_file with | Some (x,"xyz") | Some (x,"zmt") -> x^".ezfio" | _ -> xyz_file^".ezfio" end in if Sys.file_exists ezfio_file then failwith (ezfio_file^" already exists"); let write_file () = (* Create EZFIO *) Ezfio.set_file ezfio_file; (* Write Pseudo *) let pseudo = list_map (fun x -> match pseudo_channel x.Atom.element with | Some channel -> Pseudo.read_element channel x.Atom.element | None -> Pseudo.empty x.Atom.element ) nuclei in let molecule = let n_elec_to_remove = List.fold_left (fun accu x -> accu + (Positive_int.to_int x.Pseudo.n_elec)) 0 pseudo 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 (fun x -> Positive_int.to_int x.Pseudo.n_elec |> Float.of_int) pseudo |> Array.of_list in List.mapi (fun i x -> { x with Atom.charge = (Charge.to_float x.Atom.charge) -. charges.(i) |> Charge.of_float } ) molecule.Molecule.nuclei } 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 (fun x->Element.to_string x.Atom.element) nuclei and charges = list_map (fun x-> Atom.(Charge.to_float x.charge)) nuclei and coords = (list_map (fun x-> x.Atom.coord.Point3d.x) nuclei) @ (list_map (fun x-> x.Atom.coord.Point3d.y) nuclei) @ (list_map (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_left (fun accu x -> let x = List.length x.Pseudo.local in if (x > accu) then x else accu ) 0 pseudo and lmax = List.fold_left (fun accu x -> let x = List.fold_left (fun accu (x,_) -> let x = Positive_int.to_int x.Pseudo.GaussianPrimitive_non_local.proj in if (x > accu) then x else accu ) 0 x.Pseudo.non_local in if (x > accu) then x else accu ) 0 pseudo in let kmax = Array.init (lmax+1) (fun i-> list_map (fun x -> List.filter (fun (y,_) -> (Positive_int.to_int y.Pseudo.GaussianPrimitive_non_local.proj) = i) x.Pseudo.non_local |> List.length ) pseudo |> List.fold_left (fun accu x -> if accu > x then accu else x) 0 ) |> Array.fold_left (fun accu i -> if i > accu then i else accu) 0 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 klocmax nucl_num 0. , Array.make_matrix klocmax nucl_num 0. , Array.make_matrix klocmax nucl_num 0 in List.iteri (fun j x -> List.iteri (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; ) x.Pseudo.local ) pseudo ; let concat_2d tmp_array = let data = Array.map Array.to_list tmp_array |> 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) (fun _ -> (Array.make_matrix kmax nucl_num 0. )), Array.init (lmax+1) (fun _ -> (Array.make_matrix kmax nucl_num 0. )), Array.init (lmax+1) (fun _ -> (Array.make_matrix kmax nucl_num 0 )) in List.iteri (fun j x -> let last_idx = Array.make (lmax+1) 0 in List.iter (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; ) x.Pseudo.non_local ) pseudo ; let concat_3d tmp_array = let data = Array.map (fun x -> Array.map Array.to_list x |> Array.to_list |> List.concat) tmp_array |> 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 (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 Not_found -> let key = Element x.Atom.element in try Basis.read_element (basis_channel key) i e with 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; Ezfio.set_basis_basis b; let ao_prim_num = list_map (fun (_,g,_) -> List.length g.Gto.lc) long_basis and ao_nucl = list_map (fun (_,_,n) -> Nucl_number.to_int n) long_basis and ao_power= let l = list_map (fun (x,_,_) -> x) long_basis in (list_map (fun t -> Positive_int.to_int Angmom.Xyz.(t.x)) l)@ (list_map (fun t -> Positive_int.to_int Angmom.Xyz.(t.y)) l)@ (list_map (fun t -> Positive_int.to_int Angmom.Xyz.(t.z)) l) in let ao_prim_num_max = List.fold_left (fun s x -> if x > s then x else s) 0 ao_prim_num in let gtos = list_map (fun (_,x,_) -> x) long_basis in let create_expo_coef ec = let coefs = begin match ec with | `Coefs -> list_map (fun x-> list_map (fun (_,coef) -> AO_coef.to_float coef) x.Gto.lc) gtos | `Expos -> list_map (fun x-> list_map (fun (prim,_) -> AO_expo.to_float prim.GaussianPrimitive.expo) x.Gto.lc) gtos end in let rec get_n n accu = function | [] -> List.rev accu | h::tail -> let y = begin match List.nth_opt 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 () = let shell_num = List.length basis in let lc : (GaussianPrimitive.t * Qptypes.AO_coef.t) list list = list_map ( fun (g,_) -> g.Gto.lc ) basis in let ang_mom = list_map (fun (l : (GaussianPrimitive.t * Qptypes.AO_coef.t) list) -> let x, _ = List.hd l in Angmom.to_l x.GaussianPrimitive.sym |> Qptypes.Positive_int.to_int ) lc in let expo = list_map (fun l -> list_map (fun (x,_) -> Qptypes.AO_expo.to_float x.GaussianPrimitive.expo) l ) lc |> List.concat in let coef = list_map (fun l -> list_map (fun (_,x) -> Qptypes.AO_coef.to_float x) l ) lc |> List.concat in let shell_prim_num = list_map List.length lc in let shell_prim_idx = let rec aux count accu = function | [] -> List.rev accu | l::rest -> let newcount = count+(List.length l) in aux newcount (count::accu) rest in aux 1 [] lc in let prim_num = List.length coef in Ezfio.set_basis_typ "Gaussian"; Ezfio.set_basis_shell_num shell_num; Ezfio.set_basis_prim_num prim_num ; Ezfio.set_basis_shell_prim_num (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| shell_num |] ~data:shell_prim_num); Ezfio.set_basis_shell_ang_mom (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| shell_num |] ~data:ang_mom ) ; Ezfio.set_basis_shell_prim_index (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| shell_num |] ~data:shell_prim_idx) ; Ezfio.set_basis_shell_nucl (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| shell_num |] ~data:(list_map (fun (_,n) -> Nucl_number.to_int n) basis) ) ; Ezfio.set_basis_shell_prim_coef (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| prim_num |] ~data:coef) ; Ezfio.set_basis_shell_prim_expo (Ezfio.ezfio_array_of_list ~rank:1 ~dim:[| prim_num |] ~data:expo) ; 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 try if Sys.is_directory ezfio_file then rmdir ezfio_file with _ -> () end; raise ex; end in ignore @@ Sys.command ("qp_edit -c "^ezfio_file); print_endline ezfio_file let () = let open Command_line in begin "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. " |> set_description_doc ; set_header_doc (Sys.argv.(0) ^ " - Quantum Package command"); [ { opt=Optional ; short='o'; long="output"; arg=With_arg "EZFIO_DIR"; doc="Name of the created EZFIO directory."} ; { opt=Mandatory; short='b'; long="basis"; arg=With_arg ""; doc="Name of basis set file. Searched in ${QP_ROOT}/data/basis if not found."} ; { opt=Optional ; short='a'; long="au"; arg=Without_arg; doc="Input geometry is in atomic units."} ; { opt=Optional ; short='c'; long="charge"; arg=With_arg ""; doc="Total charge of the molecule. Default is 0. For negative values, use m instead of -, for ex m1"} ; { opt=Optional ; short='d'; long="dummy"; arg=With_arg ""; doc="Add dummy atoms. x * (covalent radii of the atoms)."} ; { opt=Optional ; short='m'; long="multiplicity"; arg=With_arg ""; doc="Spin multiplicity (2S+1) of the molecule. Default is 1."} ; { opt=Optional ; short='p'; long="pseudo"; arg=With_arg ""; doc="Name of the pseudopotential."} ; { opt=Optional ; short='x'; long="cartesian"; arg=Without_arg; doc="Compute AOs in the Cartesian basis set (6d, 10f, ...)."} ; anonymous "FILE" Mandatory "Input file in xyz format or z-matrix."; ] |> set_specs end; (* Handle options *) let output = Command_line.get "output" in let basis = match Command_line.get "basis" with | None -> assert false | Some x -> x in let au = Command_line.get_bool "au" in let charge = match Command_line.get "charge" with | None -> 0 | Some x -> ( if x.[0] = 'm' then ~- (int_of_string (String.sub x 1 (String.length x - 1))) else int_of_string x ) in let dummy = match Command_line.get "dummy" with | None -> 0. | Some x -> float_of_string x in let multiplicity = match Command_line.get "multiplicity" with | None -> 1 | Some n -> int_of_string n in let pseudo = Command_line.get "pseudo" in let cart = Command_line.get_bool "cartesian" in let xyz_filename = match Command_line.anon_args () with | [x] -> x | _ -> (Command_line.help () ; failwith "input file is missing") in run ?o:output basis au charge dummy multiplicity pseudo cart xyz_filename