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dipole_phi.f
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module DP_potential_m
use type_m
use constants_m
use blas95
use f95_precision
use MPI_definitions_m , only : master
use parameters_m , only : PBC , Environ_type , verbose
use MD_read_m , only : atom
use DP_FMO_m , only : DP_FMO_analysis
use Multipole_Routines_m , only : Util_Multipoles
use PBC_m , only : Generate_Periodic_DPs
public :: Dipole_Potentials , DP_phi
private
! module variables ...
type(dipoles) , save :: DP_mols_pbc
integer :: N_of_Solvent_Molecules
integer :: N_of_Solute_Molecules
! module parameters ...
real*8 , parameter :: DP_potential_factor = 2.9979255d0 ! <== e*p(Debye)/(4*Pi*epsilon_0) : eV * Angs^2; checked twice!
contains
!
!
!
!=================================
subroutine Dipole_Potentials( a )
!=================================
implicit none
type(structure) , intent(in) :: a
! local variables ...
integer :: N_of_DP_mols
type(dipoles) :: solvent , solute , DP_mols
! initialize multipole routines ...
CALL Util_Multipoles
! garbage collection before restart calculations ...
CALL DeAllocate_DPs( DP_mols_pbc , flag = "garbage" )
! solvent and solute must not overlap ...
IF( any( (a%fragment=="S") .AND. (a%solute) ) ) then
Print*, " >>> solvent and solute overlap in Environment_SetUp <<< : execution stopped"
stop
end If
If( any(a%solute) ) then
CALL Build_DP_mols( a , solvent , instance = "solvent" )
CALL Build_DP_mols( a , solute , instance = "solute" )
N_of_DP_mols = N_of_Solvent_Molecules + N_of_Solute_Molecules
CALL DeAllocate_DPs( DP_mols , N_of_DP_mols , flag = "alloc" )
DP_mols % CC( 1:N_of_Solvent_Molecules , :) = solvent % CC
DP_mols % DP( 1:N_of_Solvent_Molecules , :) = solvent % DP
DP_mols % nr( 1:N_of_Solvent_Molecules ) = solvent % nr
DP_mols % CC( N_of_Solvent_Molecules+1:N_of_DP_mols , : ) = solute % CC
DP_mols % DP( N_of_Solvent_Molecules+1:N_of_DP_mols , : ) = solute % DP
DP_mols % nr( N_of_Solvent_Molecules+1:N_of_DP_mols ) = solute % nr
CALL DeAllocate_DPs( solvent , flag = "dealloc" )
CALL DeAllocate_DPs( solute , flag = "dealloc" )
else
CALL Build_DP_mols( a , solvent , instance = "solvent" )
CALL DeAllocate_DPs( DP_mols , N_of_Solvent_Molecules , flag = "alloc" )
DP_mols = solvent
CALL DeAllocate_DPs( solvent , flag = "dealloc" )
end If
! generate periodic structure of solvent molecules ; if PBCx=PBCy=PBCz=0 ==> DP_mols_pbc = DP_mols ...
CALL Generate_Periodic_DPs( a, DP_mols%CC, DP_mols%DP, DP_mols%nr, DP_mols_pbc%CC, DP_mols_pbc%DP, DP_mols_pbc%nr )
CALL DeAllocate_DPs( DP_mols , flag = "dealloc" )
end subroutine Dipole_Potentials
!
!
!
!===================================================
subroutine Build_DP_mols( a , molecule , instance )
!===================================================
implicit none
type(structure) , intent(in) :: a
type(dipoles) , intent(out):: molecule
character(*) , intent(in) :: instance
! local variables ...
integer :: i , j , i1 , i2 , nr , last_nr , first_nr , nr_atoms , xyz
real*8 :: total_valence , Nuclear_DP(3) , Electronic_DP(3)
real*8 , allocatable :: Q_center(:,:) , DP_FMO(:,:) , Qi_Ri(:,:) , nr_vector(:,:)
! local parameters ...
real*8 , parameter :: Debye_unit = 4.803204d0
select case( instance )
case( "solvent" )
! find positions of solvent atoms in structure ...
first_nr = minval( a%nr , a%fragment == "S" )
last_nr = maxval( a%nr , a%fragment == "S" )
N_of_Solvent_Molecules = (last_nr - first_nr + 1)
! consistency check ...
If( master .AND. verbose ) Print 157 , N_of_Solvent_Molecules
case( "solute" )
! find positions of solute atoms in structure ...
first_nr = minval( a%nr , a%solute )
last_nr = maxval( a%nr , a%solute )
N_of_Solute_Molecules = (last_nr - first_nr + 1)
! consistency check ...
If( master .AND. verbose ) Print 158 , N_of_Solute_Molecules
end select
allocate(Q_center (last_nr,3) , source = 0.d0)
allocate(DP_FMO (last_nr,3) , source = 0.d0)
allocate(Qi_Ri (a%atoms,3) , source = 0.d0)
do nr = first_nr , last_nr
! No of atoms with tag nr ...
nr_atoms = count( a%nr == nr )
! position of nr residue in structure ...
i1 = minloc( a%nr , 1 , a%nr == nr )
i2 = (i1-1) + nr_atoms
!-----------------------------------------------------------------------------------------------
! calculate Center_of_Charge for each molecule: sum_i = (q_i * vec{r}_i) / sum_i q_i ...
forall( j=1:3 , i=i1:i2 ) Qi_Ri(i,j) = a%Nvalen(i) * a%coord(i,j)
total_valence = sum( [ (a%Nvalen(i) , i=i1,i2) ] )
forall(j=1:3) Q_center(nr,j) = sum( Qi_Ri(i1:i2,j) ) / total_valence
!-----------------------------------------------------------------------------------------------
! calculate the dipole vector ...
select case( Environ_type )
case( "DP_QM" )
CALL DP_FMO_analysis( a , Q_center(nr,:) , DP_FMO(nr,:) , nr )
case( "DP_MM" )
! atomic positions measured from the Center of Charge ...
allocate(nr_vector(nr_atoms,3))
forall(xyz=1:3) nr_vector(:,xyz) = a%coord(i1:i2,xyz) - Q_center(nr,xyz)
! if origin = Center_of_Charge ==> Nuclear_DP = (0,0,0)
Nuclear_DP = D_zero
! classical electronic_DP ...
forall(xyz=1:3) Electronic_DP(xyz) = sum( atom(i1:i2)%MM_charge*nr_vector(:,xyz) )
! minus sign is due to the negative electron chage ...
Electronic_DP = -Electronic_DP
DP_FMO(nr,:) = ( Nuclear_DP - Electronic_DP ) * Debye_unit
deallocate( nr_vector )
end select
!-----------------------------------------------------------------------------------------------
end do
CALL DeAllocate_DPs( molecule , last_nr-first_nr+1 , flag = "alloc" )
! NOTICE: dipole moment is multiplied by DP_potential_factor ...
do j = 1 , 3
molecule%CC( : , j ) = Q_center( first_nr:last_nr , j )
molecule%DP( : , j ) = DP_FMO ( first_nr:last_nr , j ) * DP_potential_factor
end do
! save list of nr indices for use in DP_phi ...
molecule%nr = [ ( i , i=first_nr,last_nr ) ]
deallocate( Q_center , DP_FMO , Qi_Ri )
include 'formats.h'
end subroutine Build_DP_mols
!
!
!
!===================================
pure function DP_phi( sys , a , b )
!===================================
implicit none
type(structure) , intent(in) :: sys
integer , intent(in) :: a , b
! local variables ...
integer :: i , j , N_of_DP
integer , allocatable :: nr_Mols(:)
real*8 :: hard_core , cut_off_radius , decay_cube
real*8 :: midpoint_ab(3) , aux(3)
real*8 :: DP_phi(4)
real*8 , allocatable :: distance(:) , distance_ALL(:) , mol_phi(:)
real*8 , allocatable :: vector(:,:) , versor(:,:) , vector_ALL(:,:) , decay(:,:) , DP_Mols(:,:) , mol_phi2(:,:)
logical , allocatable :: mask(:)
! local parameters ...
real*8 , parameter :: refractive_index = 1.33d0 ! <== refractive index of the solvent ...
! combination rule for solvation hardcore shell ...
hard_core = ( sys%solvation_hardcore(a) + sys%solvation_hardcore(b) ) / TWO
! midpoint between atoms a & b ...
midpoint_ab(:) = ( sys% coord(a,:) + sys% coord(b,:) ) / TWO
! total number of dipoles in PBC ...
N_of_DP = size( DP_mols_pbc%DP(:,1) )
!------------------------------------------------------------------------
! choice of solvent droplet .vs. PBC box ...
!------------------------------------------------------------------------
If( sum(PBC) == 0) then
allocate( vector ( N_of_DP , 3 ) , source = D_zero )
allocate( versor ( N_of_DP , 3 ) , source = D_zero )
allocate( DP_Mols ( N_of_DP , 3 ) , source = D_zero )
allocate( decay ( N_of_DP , 3 ) , source = D_zero )
allocate( distance( N_of_DP ) , source = D_zero )
allocate( mol_phi ( N_of_DP ) , source = D_zero )
allocate( nr_Mols ( N_of_DP ) , source = I_zero )
do i = 1 , N_of_DP
vector(i,:) = midpoint_ab(:) - DP_mols_pbc%CC(i,:)
distance(i) = sqrt( sum( vector(i,:)*vector(i,:) ) )
versor(i,:) = vector(i,:) / distance(i)
end do
DP_Mols = DP_mols_pbc%DP
nr_Mols = DP_mols_pbc%nr
else
! maximum distance from midpoint a-b ...
cut_off_radius = minval(sys% T_xyz) / TWO
allocate( vector_ALL ( N_of_DP , 3 ) , source = D_zero )
allocate( distance_ALL ( N_of_DP ) , source = D_zero )
allocate( mask ( N_of_DP ) , source = .false. )
do i = 1 , N_of_DP
vector_ALL(i,:) = midpoint_ab(:) - DP_mols_pbc%CC(i,:)
distance_ALL(i) = sqrt( dot_product( vector_ALL(i,:),vector_ALL(i,:) ) )
end do
mask = ( (distance_ALL > hard_core) .AND. (distance_ALL < cut_off_radius) )
! redefine range of interaction with molecules inside cut_off radius ...
N_of_DP = count( mask )
allocate( vector ( N_of_DP , 3 ) , source = D_zero )
allocate( versor ( N_of_DP , 3 ) , source = D_zero )
allocate( DP_Mols ( N_of_DP , 3 ) , source = D_zero )
allocate( decay ( N_of_DP , 3 ) , source = D_zero )
allocate( distance( N_of_DP ) , source = D_zero )
allocate( mol_phi ( N_of_DP ) , source = D_zero )
allocate( nr_Mols ( N_of_DP ) , source = I_zero )
do j = 1 , 3
vector(:,j) = pack( vector_ALL(:,j) , mask , vector(:,j) )
DP_Mols(:,j) = pack( DP_mols_pbc%DP(:,j) , mask , DP_Mols(:,j) )
end do
nr_Mols = pack( DP_mols_pbc%nr , mask , nr_Mols )
distance = pack( distance_ALL , mask , distance )
forall( i=1:N_of_DP ) versor(i,:) = vector(i,:) / distance(i)
deallocate( vector_ALL , distance_ALL , mask )
end if
!------------------------------------------------------------------------
! calculate dipole potential at a-b midpoint ...
!------------------------------------------------------------------------
allocate( mol_phi2( N_of_DP , 3 ) , source = D_zero )
do i = 1 , N_of_DP
decay_cube = D_one / (distance(i)*distance(i)*distance(i))
! first order ...
decay(i,:) = vector(i,:) * decay_cube
! DP_potential due to dipole i ...
mol_phi(i) = dot_product( DP_Mols(i,:),decay(i,:) )
! second order ...
aux(:) = DP_Mols(i,:) - THREE * dot_product(DP_Mols(i,:),versor(i,:)) * versor(i,:)
mol_phi2(i,:) = aux(:) * decay_cube
end do
! excluding self-interaction ...
where( (nr_Mols == sys%nr(a)) .OR. (nr_Mols == sys%nr(b)) )
mol_phi = 0.d0
mol_phi2(:,1) = 0.d0
mol_phi2(:,2) = 0.d0
mol_phi2(:,3) = 0.d0
end where
! first order ...
DP_phi(1) = sum( mol_phi )
! second order ...
forall( j=1:3 ) DP_phi(j+1) = sum( mol_phi2(:,j) )
! applying optical dielectric screening ...
DP_phi = DP_phi / (refractive_index)**2
deallocate( vector , decay , distance , DP_Mols , nr_Mols , mol_phi , mol_phi2 )
end function DP_phi
!
!
!
!
!===========================================
subroutine DeAllocate_DPs( DPs , n , flag )
!===========================================
implicit none
type(dipoles) , intent(inout) :: DPs
integer , optional , intent(in) :: n
character(*) , intent(in) :: flag
select case( flag )
case( "alloc" )
allocate( DPs%CC ( n , 3 ) , source = D_zero )
allocate( DPs%DP ( n , 3 ) , source = D_zero )
allocate( DPs%nr ( n ) , source = I_zero )
case( "dealloc" )
deallocate( DPs%CC )
deallocate( DPs%DP )
deallocate( DPs%nr )
case( "garbage" )
! garbage collection before restart calculations ...
If( allocated( DPs%CC ) ) deallocate( DPs%CC )
If( allocated( DPs%DP ) ) deallocate( DPs%DP )
If( allocated( DPs%nr ) ) deallocate( DPs%nr )
end select
end subroutine DeAllocate_DPs
!
!
!
end module DP_potential_m