mirror of
https://gitlab.com/scemama/QCaml.git
synced 2024-09-01 17:23:41 +02:00
523 lines
17 KiB
OCaml
523 lines
17 KiB
OCaml
open Util
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module Am = AngularMomentum
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module Asp = AtomicShellPair
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module Aspc = AtomicShellPairCouple
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module Co = Coordinate
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module Cs = ContractedShell
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module Csp = ContractedShellPair
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module Cspc = ContractedShellPairCouple
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module Po = Powers
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module Psp = PrimitiveShellPair
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module Pspc = PrimitiveShellPairCouple
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module Ps = PrimitiveShell
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module Zp = Zero_m_parameters
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let cutoff = Constants.integrals_cutoff
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let cutoff2 = cutoff *. cutoff
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exception NullQuartet
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type four_idx_intermediates =
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{
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expo_b : float ;
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expo_d : float ;
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expo_p_inv : float ;
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expo_q_inv : float ;
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center_ab : Co.t ;
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center_cd : Co.t ;
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center_pq : Co.t ;
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center_pa : Co.t ;
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center_qc : Co.t ;
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zero_m_array : float array ;
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}
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(** Horizontal and Vertical Recurrence Relations (HVRR) *)
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let rec hvrr_two_e
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angMom_a angMom_b angMom_c angMom_d
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abcd map_1d map_2d =
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(* Swap electrons 1 and 2 so that the max angular momentum is on 1 *)
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if angMom_a.Po.tot + angMom_b.Po.tot < angMom_c.Po.tot + angMom_d.Po.tot then
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let abcd = {
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expo_b = abcd.expo_d ;
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expo_d = abcd.expo_b ;
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expo_p_inv = abcd.expo_q_inv ;
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expo_q_inv = abcd.expo_p_inv ;
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center_ab = abcd.center_cd ;
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center_cd = abcd.center_ab ;
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center_pq = Co.neg abcd.center_pq ;
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center_pa = abcd.center_qc ;
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center_qc = abcd.center_pa ;
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zero_m_array = abcd.zero_m_array ;
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} in
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hvrr_two_e
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angMom_c angMom_d angMom_a angMom_b
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abcd map_1d map_2d
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else
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let maxm = angMom_a.Po.tot + angMom_b.Po.tot + angMom_c.Po.tot + angMom_d.Po.tot in
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let maxsze = maxm+1 in
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let get_xyz angMom =
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match angMom with
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| { Po.y=0 ; z=0 ; _ } -> Co.X
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| { z=0 ; _ } -> Co.Y
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| _ -> Co.Z
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in
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let expo_p_inv = abcd.expo_p_inv
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and expo_q_inv = abcd.expo_q_inv
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and center_ab = abcd.center_ab
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and center_cd = abcd.center_cd
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and center_pq = abcd.center_pq
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in
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(** Vertical recurrence relations *)
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let rec vrr0 angMom_a =
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match angMom_a.Po.tot with
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| 0 -> abcd.zero_m_array
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| _ ->
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let key = Zkey.of_powers_three angMom_a in
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try Zmap.find map_1d key with
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| Not_found ->
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let result =
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let xyz = get_xyz angMom_a in
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let am = Po.decr xyz angMom_a in
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let amxyz = Po.get xyz am in
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let f1 = expo_p_inv *. Co.get xyz center_pq
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and f2 = abcd.expo_b *. expo_p_inv *. Co.get xyz center_ab
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in
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let result = Array.create_float (maxsze - angMom_a.Po.tot) in
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if amxyz = 0 then
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begin
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let v1 = vrr0 am in
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Array.iteri (fun m _ ->
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result.(m) <- f1 *. v1.(m+1) -. f2 *. v1.(m)) result
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end
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else
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begin
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let amm = Po.decr xyz am in
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let v3 = vrr0 amm in
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let v1 = vrr0 am in
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let f3 = (float_of_int_fast amxyz) *. expo_p_inv *. 0.5 in
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Array.iteri (fun m _ ->
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result.(m) <- f1 *. v1.(m+1) -. f2 *. v1.(m)
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+. f3 *. (v3.(m) +. expo_p_inv *. v3.(m+1)) ) result
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end;
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result
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in Zmap.add map_1d key result;
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result
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and vrr angMom_a angMom_c =
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match angMom_a.Po.tot, angMom_c.Po.tot with
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| (i,0) -> if (i>0) then vrr0 angMom_a
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else abcd.zero_m_array
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| (_,_) ->
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let key = Zkey.of_powers_six angMom_a angMom_c in
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try Zmap.find map_2d key with
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| Not_found ->
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let result =
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(* angMom_c.Po.tot > 0 so cm.Po.tot >= 0 *)
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let xyz = get_xyz angMom_c in
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let cm = Po.decr xyz angMom_c in
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let cmxyz = Po.get xyz cm in
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let axyz = Po.get xyz angMom_a in
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let f1 =
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-. abcd.expo_d *. expo_q_inv *. Co.get xyz center_cd
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and f2 =
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expo_q_inv *. Co.get xyz center_pq
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in
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let result = Array.make (maxsze - angMom_a.Po.tot - angMom_c.Po.tot) 0. in
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if axyz > 0 then
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begin
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let am = Po.decr xyz angMom_a in
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let f5 =
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(float_of_int_fast axyz) *. expo_p_inv *. expo_q_inv *. 0.5
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in
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if (abs_float f5 > cutoff) then
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let v5 =
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vrr am cm
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in
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Array.iteri (fun m _ ->
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result.(m) <- result.(m) -. f5 *. v5.(m+1)) result
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end;
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if cmxyz > 0 then
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begin
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let f3 =
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(float_of_int_fast cmxyz) *. expo_q_inv *. 0.5
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in
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if (abs_float f3 > cutoff) ||
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(abs_float (f3 *. expo_q_inv) > cutoff) then
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begin
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let v3 =
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let cmm = Po.decr xyz cm in
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vrr angMom_a cmm
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in
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Array.iteri (fun m _ ->
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result.(m) <- result.(m) +.
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f3 *. (v3.(m) +. expo_q_inv *. v3.(m+1)) ) result
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end
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end;
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if ( (abs_float f1 > cutoff) || (abs_float f2 > cutoff) ) then
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begin
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let v1 =
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vrr angMom_a cm
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in
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Array.iteri (fun m _ ->
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result.(m) <- result.(m) +. f1 *. v1.(m) -. f2 *. v1.(m+1) ) result
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end;
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result
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in Zmap.add map_2d key result;
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result
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(*
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and trr angMom_a angMom_c =
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match (angMom_a.Po.tot, angMom_c.Po.tot) with
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| (i,0) -> if (i>0) then (vrr0 angMom_a).(0)
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else abcd.zero_m_array.(0)
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| (_,_) ->
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let key = Zkey.of_powers_six angMom_a angMom_c in
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try (Zmap.find map_2d key).(0) with
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| Not_found ->
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let result =
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let xyz = get_xyz angMom_c in
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let axyz = Po.get xyz angMom_a in
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let cm = Po.decr xyz angMom_c in
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let cmxyz = Po.get xyz cm in
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let expo_inv_q_over_p = expo_q_inv /. expo_p_inv in
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let f =
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Co.get xyz center_qc +. expo_inv_q_over_p *.
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Co.get xyz center_pa
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in
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let result = 0. in
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let result =
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if cmxyz < 1 then result else
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let f = 0.5 *. (float_of_int_fast cmxyz) *. expo_q_inv in
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if abs_float f < cutoff then 0. else
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let cmm = Po.decr xyz cm in
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let v3 = trr angMom_a cmm in
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result +. f *. v3
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in
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let result =
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if abs_float f < cutoff then result else
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let v1 = trr angMom_a cm in
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result +. f *. v1
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in
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let result =
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if cmxyz < 0 then result else
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let f = -. expo_inv_q_over_p in
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let ap = Po.incr xyz angMom_a in
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let v4 = trr ap cm in
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result +. v4 *. f
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in
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let result =
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if axyz < 1 then result else
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let f = 0.5 *. (float_of_int_fast axyz) *. expo_q_inv in
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if abs_float f < cutoff then result else
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let am = Po.decr xyz angMom_a in
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let v2 = trr am cm in
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result +. f *. v2
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in
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result
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in
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Zmap.add map_2d key [|result|];
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result
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*)
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in
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let vrr a c =
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(vrr a c).(0)
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(*
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if maxm < 10 then (vrr a c).(0) else trr a c
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*)
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in
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(** Horizontal recurrence relations *)
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let rec hrr0 angMom_a angMom_b angMom_c =
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match angMom_b.Po.tot with
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| 1 ->
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let xyz = get_xyz angMom_b in
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let ap = Po.incr xyz angMom_a in
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let v1 = vrr ap angMom_c in
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let f2 = Co.get xyz center_ab in
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if (abs_float f2 < cutoff) then v1 else
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let v2 = vrr angMom_a angMom_c in
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v1 +. f2 *. v2
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| 0 -> vrr angMom_a angMom_c
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| _ ->
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let xyz = get_xyz angMom_b in
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let bxyz = Po.get xyz angMom_b in
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if bxyz > 0 then
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let ap = Po.incr xyz angMom_a in
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let bm = Po.decr xyz angMom_b in
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let h1 = hrr0 ap bm angMom_c in
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let f2 = Co.get xyz center_ab in
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if abs_float f2 < cutoff then h1 else
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let h2 = hrr0 angMom_a bm angMom_c in
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h1 +. f2 *. h2
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else 0.
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and hrr angMom_a angMom_b angMom_c angMom_d =
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match (angMom_b.Po.tot, angMom_d.Po.tot) with
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| (_,0) ->
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if (angMom_b.Po.tot = 0) then
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vrr angMom_a angMom_c
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else
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hrr0 angMom_a angMom_b angMom_c
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| (_,_) ->
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let xyz = get_xyz angMom_d in
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let cp = Po.incr xyz angMom_c in
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let dm = Po.decr xyz angMom_d in
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let h1 = hrr angMom_a angMom_b cp dm in
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let f2 = Co.get xyz center_cd in
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if abs_float f2 < cutoff then h1 else
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let h2 = hrr angMom_a angMom_b angMom_c dm in
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h1 +. f2 *. h2
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in
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hrr angMom_a angMom_b angMom_c angMom_d
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let contracted_class_shell_pair_couple ~basis ~zero_m shell_pair_couple : float Zmap.t =
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let maxm = Am.to_int (Cspc.ang_mom shell_pair_couple) in
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(* Pre-computation of integral class indices *)
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let class_indices = Cspc.zkey_array shell_pair_couple in
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let contracted_class =
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Array.make (Array.length class_indices) 0.;
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in
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let monocentric =
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Cspc.monocentric shell_pair_couple
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in
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(* Compute all integrals in the shell for each pair of significant shell pairs *)
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let shell_p = Cspc.shell_pair_p shell_pair_couple
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and shell_q = Cspc.shell_pair_q shell_pair_couple
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in
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let center_ab = Csp.a_minus_b shell_p
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and center_cd = Csp.a_minus_b shell_q
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in
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let norm_scales = Cspc.norm_scales shell_pair_couple in
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List.iter (fun (coef_prod, spc) ->
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let sp_ab = Pspc.shell_pair_p spc
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and sp_cd = Pspc.shell_pair_q spc
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in
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let center_pq = Co.(Psp.center sp_ab |- Psp.center sp_cd) in
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let center_pa = Psp.center_minus_a sp_ab in
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let center_qc = Psp.center_minus_a sp_cd in
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let norm_pq_sq = Co.dot center_pq center_pq in
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let expo_p_inv = Psp.exponent_inv sp_ab in
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let expo_q_inv = Psp.exponent_inv sp_cd in
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let zero = Zp.zero basis zero_m in
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let zero_m_array = zero_m
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{ zero with
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maxm ; expo_p_inv ; expo_q_inv ; norm_pq_sq ;
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center_pq ; center_pa ; center_qc ;
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}
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in
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begin
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match Cspc.ang_mom shell_pair_couple with
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| Am.S ->
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let integral = zero_m_array.(0) in
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contracted_class.(0) <- contracted_class.(0) +. coef_prod *. integral
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| _ ->
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let expo_b = Ps.exponent (Psp.shell_b sp_ab)
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and expo_d = Ps.exponent (Psp.shell_b sp_cd)
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in
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let map_1d = Zmap.create (4*maxm)
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and map_2d = Zmap.create (Array.length class_indices)
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in
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(* Compute the integral class from the primitive shell quartet *)
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class_indices
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|> Array.iteri (fun i key ->
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let (angMom_a,angMom_b,angMom_c,angMom_d) =
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match Zkey.to_powers key with
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| Zkey.Twelve x -> x
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| _ -> assert false
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in
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try
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if monocentric then
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begin
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if ( ((1 land angMom_a.Po.x + angMom_b.Po.x + angMom_c.Po.x + angMom_d.Po.x)=1) ||
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((1 land angMom_a.Po.y + angMom_b.Po.y + angMom_c.Po.y + angMom_d.Po.y)=1) ||
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((1 land angMom_a.Po.z + angMom_b.Po.z + angMom_c.Po.z + angMom_d.Po.z)=1)
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) then
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raise NullQuartet
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end;
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let norm = norm_scales.(i) in
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let coef_prod = coef_prod *. norm in
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let abcd = {
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expo_b ; expo_d ; expo_p_inv ; expo_q_inv ;
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center_ab ; center_cd ; center_pq ;
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center_pa ; center_qc ; zero_m_array ;
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} in
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let integral =
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hvrr_two_e
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angMom_a angMom_b angMom_c angMom_d
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abcd map_1d map_2d
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in
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contracted_class.(i) <- contracted_class.(i) +. coef_prod *. integral
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with NullQuartet -> ()
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)
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end
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) (Cspc.coefs_and_shell_pair_couples shell_pair_couple);
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let result =
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Zmap.create (Array.length contracted_class)
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in
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Array.iteri (fun i key -> Zmap.add result key contracted_class.(i)) class_indices;
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result
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let contracted_class_atomic_shell_pair_couple ~basis ~zero_m atomic_shell_pair_couple : float Zmap.t =
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let maxm = Am.to_int (Aspc.ang_mom atomic_shell_pair_couple) in
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(* Pre-computation of integral class indices *)
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let class_indices = Aspc.zkey_array atomic_shell_pair_couple in
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let contracted_class =
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Array.make (Array.length class_indices) 0.;
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in
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let monocentric =
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Aspc.monocentric atomic_shell_pair_couple
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in
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let shell_p = Aspc.atomic_shell_pair_p atomic_shell_pair_couple
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and shell_q = Aspc.atomic_shell_pair_q atomic_shell_pair_couple
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in
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(* Compute all integrals in the shell for each pair of significant shell pairs *)
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let center_ab = Asp.a_minus_b shell_p
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and center_cd = Asp.a_minus_b shell_q
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in
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let norm_scales = Aspc.norm_scales atomic_shell_pair_couple in
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List.iter (fun cspc ->
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List.iter (fun (coef_prod, spc) ->
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let sp_ab = Pspc.shell_pair_p spc
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and sp_cd = Pspc.shell_pair_q spc
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in
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let expo_p_inv = Psp.exponent_inv sp_ab
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in
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let center_pq = Co.(Psp.center sp_ab |- Psp.center sp_cd) in
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let center_qc = Psp.center_minus_a sp_cd in
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let center_pa = Psp.center_minus_a sp_ab in
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let norm_pq_sq = Co.dot center_pq center_pq in
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let expo_q_inv = Psp.exponent_inv sp_cd in
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let zero = Zp.zero basis zero_m in
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let zero_m_array = zero_m
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{ zero with
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maxm ; expo_p_inv ; expo_q_inv ; norm_pq_sq ;
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center_pq ; center_pa ; center_qc ;
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}
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in
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begin
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match Aspc.ang_mom atomic_shell_pair_couple with
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| Am.S ->
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let integral = zero_m_array.(0) in
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contracted_class.(0) <- contracted_class.(0) +. coef_prod *. integral
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| _ ->
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let expo_b = Ps.exponent (Psp.shell_b sp_ab)
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and expo_d = Ps.exponent (Psp.shell_b sp_cd)
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in
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let map_1d = Zmap.create (4*maxm)
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and map_2d = Zmap.create (Array.length class_indices)
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in
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(* Compute the integral class from the primitive shell quartet *)
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class_indices
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|> Array.iteri (fun i key ->
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let (angMom_a,angMom_b,angMom_c,angMom_d) =
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match Zkey.to_powers key with
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| Zkey.Twelve x -> x
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| _ -> assert false
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in
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try
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if monocentric then
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begin
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if ( ((1 land angMom_a.Po.x + angMom_b.Po.x + angMom_c.Po.x + angMom_d.Po.x)=1) ||
|
|
((1 land angMom_a.Po.y + angMom_b.Po.y + angMom_c.Po.y + angMom_d.Po.y)=1) ||
|
|
((1 land angMom_a.Po.z + angMom_b.Po.z + angMom_c.Po.z + angMom_d.Po.z)=1)
|
|
) then
|
|
raise NullQuartet
|
|
end;
|
|
|
|
let norm = norm_scales.(i) in
|
|
let coef_prod = coef_prod *. norm in
|
|
|
|
let abcd = {
|
|
expo_b ; expo_d ; expo_p_inv ; expo_q_inv ;
|
|
center_ab ; center_cd ; center_pq ;
|
|
center_pa ; center_qc ; zero_m_array ;
|
|
} in
|
|
let integral =
|
|
hvrr_two_e
|
|
angMom_a angMom_b angMom_c angMom_d
|
|
abcd
|
|
map_1d map_2d
|
|
in
|
|
contracted_class.(i) <- contracted_class.(i) +. coef_prod *. integral
|
|
with NullQuartet -> ()
|
|
)
|
|
end
|
|
) (Cspc.coefs_and_shell_pair_couples cspc)
|
|
) (Aspc.contracted_shell_pair_couples atomic_shell_pair_couple);
|
|
|
|
let result =
|
|
Zmap.create (Array.length contracted_class)
|
|
in
|
|
Array.iteri (fun i key -> Zmap.add result key contracted_class.(i)) class_indices;
|
|
result
|
|
|