Prepare cosmo implementation for use with post scf methods. (#666)

grimme-lab · Jul 13, 2022 · 9096eee · 9096eee
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diff --git a/include/param_cosmo.fh b/include/param_cosmo.fh
@@ -0,0 +1,66 @@
+type(gbsa_parameter),parameter :: gfn_cosmo = gbsa_parameter ( &
+    76.36000000_wp, &
+    18.00000000_wp, &
+     1.00000000_wp, &
+     1.00000000_wp, &
+     1.30000000_wp, &
+     0.00000000_wp, &
+     0.00000000_wp, &
+     0.00000000_wp, &
+   (/ -0.08499967_wp,   0.46780225_wp,  -2.87013596_wp,  -3.95935069_wp,  -0.29783987_wp, &
+      -0.48323273_wp,   0.00133622_wp,   0.20448945_wp,   0.20150600_wp,   0.36379863_wp, &
+      -3.47082133_wp,  -0.93451053_wp,  -1.46342018_wp,  -0.32774697_wp,  -0.38015204_wp, &
+      -0.35311116_wp,  -0.19972593_wp,  -0.12891363_wp,  -1.19450558_wp,  -1.61289300_wp, &
+      -4.68022533_wp,   3.22705056_wp,  -1.76349679_wp,  -1.78246886_wp,  -1.41389733_wp, &
+      -2.03424961_wp, -13.15585203_wp,  -0.60232543_wp,  -0.51255518_wp,  -1.05389890_wp, &
+      -0.80992362_wp,  -0.04534252_wp,  -0.48402589_wp,  -0.34738945_wp,  -0.31467674_wp, &
+      -0.13545936_wp,  -1.19984632_wp,  -1.57439157_wp,  -7.77905850_wp,  -0.25386776_wp, &
+      -1.36181862_wp,  -1.89986750_wp,  -1.66264106_wp,   0.63693473_wp,  -0.42449931_wp, &
+      -0.73041159_wp,  -0.48383194_wp,  -0.60860050_wp,  -1.34579404_wp,  -0.28314431_wp, &
+      -0.58997478_wp,  -0.50506060_wp,  -0.36680822_wp,  -0.28828614_wp,  -1.50384745_wp, &
+      -1.72772005_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,  -0.95945946_wp,  -0.97138135_wp,  -2.83432331_wp,  -2.01934203_wp, &
+      -1.19296724_wp,  -0.73245256_wp,  -0.58420150_wp,  -0.43386368_wp,  -0.70607621_wp, &
+      -0.73268812_wp,  -1.00876694_wp,  -0.52518304_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp /), &
+   (/  0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp,   0.30000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp, &
+       0.80000000_wp,   0.80000000_wp,   0.80000000_wp,   0.80000000_wp /), &
+   (/  0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp, &
+       0.00000000_wp,   0.00000000_wp,   0.00000000_wp,   0.00000000_wp /) )
diff --git a/src/param/CMakeLists.txt b/src/param/CMakeLists.txt
@@ -22,6 +22,7 @@ list(APPEND srcs
   "${dir}/paulingen.f90"
   "${dir}/sqrtzr4r2.f90"
   "${dir}/vdwradd3.f90"
+  "${dir}/vdwradcosmo.f90"
 )
 
 set(srcs ${srcs} PARENT_SCOPE)
diff --git a/src/param/meson.build b/src/param/meson.build
@@ -20,4 +20,5 @@ srcs += files(
   'paulingen.f90',
   'sqrtzr4r2.f90',
   'vdwradd3.f90',
+  'vdwradcosmo.f90',
 )
diff --git a/src/param/vdwradcosmo.f90 b/src/param/vdwradcosmo.f90
@@ -0,0 +1,103 @@
+! This file is part of xtb.
+!
+! Copyright (C) 2019-2020 Sebastian Ehlert
+!
+! xtb is free software: you can redistribute it and/or modify it under
+! the terms of the GNU Lesser General Public License as published by
+! the Free Software Foundation, either version 3 of the License, or
+! (at your option) any later version.
+!
+! xtb is distributed in the hope that it will be useful,
+! but WITHOUT ANY WARRANTY; without even the implied warranty of
+! MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE.  See the
+! GNU Lesser General Public License for more details.
+!
+! You should have received a copy of the GNU Lesser General Public License
+! along with xtb.  If not, see <https://www.gnu.org/licenses/>.
+
+!> Cosmo van-der-Waals radii
+
+module xtb_param_vdwradcosmo
+   use xtb_mctc_accuracy, only : wp
+   use xtb_mctc_convert, only : aatoau
+   use xtb_mctc_symbols, only : toNumber
+   implicit none
+   private
+
+   public :: getVanDerWaalsRadCosmo, vanDerWaalsRadCosmo
+
+
+   !> Get van-der-Waals Rad for a species
+   interface getVanDerWaalsRadCosmo
+      module procedure :: getVanDerWaalsRadCosmoSymbol
+      module procedure :: getVanDerWaalsRadCosmoNumber
+   end interface getVanDerWaalsRadCosmo
+
+
+   !> Default value for unoptimized van-der-Waals radii
+   real(wp), parameter :: cosmostub = 2.223_wp
+
+   !> COSMO optimized van-der-Waals radii
+   real(wp), parameter :: vanDerWaalsRadCosmo(94) = aatoau * [ &
+       & 1.3000_wp, 1.6380_wp, 1.5700_wp, 1.0530_wp, &   ! h-be
+       & 2.0480_wp, 2.0000_wp, 1.8300_wp, 1.7200_wp, &   ! B-O
+       & 1.7200_wp, 1.8018_wp, 1.8000_wp, 1.6380_wp, &   ! F-Mg
+       & 2.1530_wp, 2.2000_wp, 2.1060_wp, 2.1600_wp, &   ! Al-S
+       & 2.0500_wp, 2.2000_wp, 2.2230_wp, cosmostub, &   ! Cl-Ca
+       & cosmostub, 2.2930_wp, cosmostub, cosmostub, &   ! Sc-Cr
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Mn-Ni
+       & cosmostub, 1.6260_wp, cosmostub, 2.7000_wp, &   ! Cu-Ge
+       & 2.3500_wp, 2.2000_wp, 2.1600_wp, 2.3630_wp, &   ! As-Kr
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Rb-Zr
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Nb-Ru
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Rh-Cd
+       & 2.2580_wp, 2.5500_wp, 2.4100_wp, 2.4100_wp, &   ! In-Te
+       & 2.3200_wp, 2.5270_wp, cosmostub, cosmostub, &   ! I-Ba
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! La-Nd
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Pm-Gd
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Tb-Er
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Tm-Hf
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Ta-Os
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Ir-Hg
+       & cosmostub, 2.3600_wp, 2.4220_wp, 2.3050_wp, &   ! Tl-Po
+       & 2.3630_wp, 2.5740_wp, cosmostub, cosmostub, &   ! At-Ra
+       & cosmostub, cosmostub, cosmostub, cosmostub, &   ! Ac-U
+       & cosmostub, cosmostub]                           ! Np-Pu
+
+
+contains
+
+
+!> Get van-der-Waals radius for species with a given symbol
+elemental function getVanDerWaalsRadCosmoSymbol(symbol) result(rad)
+
+   !> Element symbol
+   character(len=*), intent(in) :: symbol
+
+   !> van-der-Waals radius
+   real(wp) :: rad
+
+   rad = getVanDerWaalsRadCosmo(toNumber(symbol))
+
+end function getVanDerWaalsRadCosmoSymbol
+
+
+!> Get van-der-Waals radius for species with a given atomic number
+elemental function getVanDerWaalsRadCosmoNumber(number) result(rad)
+
+   !> Atomic number
+   integer, intent(in) :: number
+
+   !> van-der-Waals radius
+   real(wp) :: rad
+
+   if (number > 0 .and. number <= size(vanDerWaalsRadCosmo, dim=1)) then
+      rad = vanDerWaalsRadCosmo(number)
+   else
+      rad = -1.0_wp
+   end if
+
+end function getVanDerWaalsRadCosmoNumber
+
+
+end module xtb_param_vdwradcosmo
diff --git a/src/solv/model.f90 b/src/solv/model.f90
@@ -1,3 +1,4 @@
+
 ! This file is part of xtb.
 !
 ! Copyright (C) 2019-2020 Sebastian Ehlert
@@ -23,13 +24,15 @@ module xtb_solv_model
    use xtb_mctc_strings, only : lowercase
    use xtb_mctc_systools, only : rdpath
    use xtb_param_vdwradd3, only : vanDerWaalsRadD3
+   use xtb_param_vdwradcosmo, only : vanDerWaalsRadCosmo
    use xtb_solv_gbsa, only : TBorn, init_ => init
    use xtb_solv_cosmo, only : TCosmo, init_ => init
    use xtb_solv_input, only : TSolvInput
    use xtb_solv_kernel, only : gbKernel
    use xtb_solv_state, only : solutionState, getStateShift
    use xtb_type_environment, only : TEnvironment
    use xtb_type_solvation, only : TSolvation
+   use ieee_arithmetic, only : ieee_value,ieee_positive_inf
    implicit none
    private
 
@@ -143,6 +146,8 @@ module xtb_solv_model
    include 'param_alpb_methanol.fh'
    include 'param_alpb_ethanol.fh'
 
+   include 'param_cosmo.fh'
+
    !> Solvent density (g/cm^3) and molar mass (g/mol)
    real(wp), parameter :: molcm3toau = 8.92388e-2_wp
 
@@ -191,7 +196,7 @@ subroutine initSolvModel(self, env, input, level)
       call getParamFile(env, solvent, 'cosmo', level, self%paramFile)
    end if
 
-   if (.not.allocated(self%paramFile)) then
+   if (.not.allocated(self%paramFile) .and. (.not.input%cosmo)) then
       call getParamFile(env, solvent, 'gbsa', level, self%paramFile)
    end if
 
@@ -238,7 +243,12 @@ subroutine loadInternalParam(self, env, solvent, level)
    !> Method level for solvation model
    integer, intent(in) :: level
 
-   type(gbsa_parameter), allocatable :: param
+   !> I/O handling
+
+   integer :: iostat
+
+   type(gbsa_parameter), allocatable :: param, stub
+
 
    select case(self%kernel)
    case (gbKernel%still)
@@ -376,6 +386,34 @@ subroutine loadInternalParam(self, env, solvent, level)
             param = gfn1_alpb_hexane
          end select
       end if
+
+      if (self%cosmo) then
+         if (allocated(param)) then
+            self%paramFile = self%paramFile//"+COSMO"
+            stub = param
+            param = gfn_cosmo
+            param%epsv = stub%epsv
+            param%smass = stub%smass
+            param%rhos = stub%rhos
+            param%gamscale = stub%gamscale
+         else if ((solvent .eq. "inf") .or. (solvent .eq. "infinity")) then
+            self%paramFile = "internal GFN-xTB/COSMO"
+            param = gfn_cosmo
+            param%epsv = ieee_value(param%epsv,ieee_positive_inf)
+         else
+            self%paramFile = "internal GFN-xTB/COSMO"
+            param = gfn_cosmo
+            read(solvent,*,iostat=iostat) param%epsv
+            if (iostat .ne. 0) then
+               Call env%error(solvent// " is neither a solvent name nor a dielectric constant.",source)
+               return
+            end if
+            if (param%epsv .eq. 0) then
+               Call env%error("You really chose 0 as your dielectric constant?",source)
+               return
+            end if
+         end if
+      end if
 
       if (.not.allocated(param)) then
          call env%error("solvent: '"//solvent//"' is not parametrized", source)
@@ -459,7 +497,12 @@ subroutine paramToModel(self, param)
    self%bornOffset = param%soset * 0.1_wp*aatoau
    self%probeRad = param%rprobe * aatoau
 
-   self%vdwRad = vanDerWaalsRadD3
+   if (self%cosmo) then
+      self%vdwRad=vanDerWaalsRadCosmo
+   else
+      self%vdwRad=vanDerWaalsRadD3
+   end if
+
    self%surfaceTension = param%gamscale * fourpi*surfaceTension
    self%descreening = param%sx
    allocate(self%hBondStrength(size(param%tmp)))

diff --git a/test/unit/test_gfn1.f90 b/test/unit/test_gfn1.f90
@@ -874,23 +874,23 @@ subroutine test_gfn1_mindless_cosmo(error)
       & "h2o", "chcl3", "thf", "acetonitrile", "toluene", &
       & "ch2cl2", "ether", "methanol", "cs2", "dmso"]
    real(wp), parameter :: ref_energies(10) = &
-      &[-33.068149119769_wp,-26.879297949029_wp,-25.848339775486_wp, &
-      & -24.920550779459_wp,-29.057643142396_wp,-20.616717615153_wp, &
-      & -35.781900213083_wp,-33.108563594503_wp,-21.434739333961_wp, &
-      & -26.668994477103_wp]
+      &[-33.086826283006_wp,-26.892421337119_wp,-25.862366080135_wp, &
+      & -24.929812068243_wp,-29.068535381601_wp,-20.631250827831_wp, &
+      & -35.780608195840_wp,-33.119209493948_wp,-21.444833411574_wp, &
+      & -26.674508354162_wp]
    real(wp), parameter :: ref_gnorms(10) = &
-      &[0.048610989970_wp, 0.061037608875_wp, 0.051110430194_wp, &
-      & 0.093510458216_wp, 0.048462578319_wp, 0.056499605067_wp, &
-      & 0.062179565785_wp, 0.060672469106_wp, 0.041589454825_wp, &
-      & 0.042982140079_wp]
+      &[0.056910263744_wp, 0.059732400683_wp, 0.052197041661_wp, &
+      & 0.097844384419_wp, 0.047961348424_wp, 0.057230114090_wp, &
+      & 0.060889237549_wp, 0.068600226343_wp, 0.042102755940_wp, &
+      & 0.042610278777_wp]
    real(wp), parameter :: ref_hlgaps(10) = &
-      &[3.512016853496_wp, 1.675002766293_wp, 2.500980871958_wp, &
-      & 1.659094616440_wp, 2.420893146112_wp, 3.802456715570_wp, &
-      & 2.599886803836_wp, 1.354752587871_wp, 4.107155093819_wp, &
-      & 1.379801456095_wp]
+      &[3.560961680882_wp, 1.701178515210_wp, 2.575575698307_wp, &
+      & 1.642444939544_wp, 2.389954524574_wp, 3.624912973388_wp, &
+      & 2.770751688023_wp, 1.357191094207_wp, 4.102623151933_wp, &
+      & 1.391461153653_wp]
 
    call init(env)
-   do iMol = 1, 2
+   do iMol = 1,10
 
       call getMolecule(mol, mindless(iMol))
 

diff --git a/test/unit/test_gfn2.f90 b/test/unit/test_gfn2.f90
@@ -793,23 +793,23 @@ subroutine test_gfn2_mindless_cosmo(error)
       & "h2o", "chcl3", "thf", "acetonitrile", "toluene", &
       & "ch2cl2", "ether", "methanol", "cs2", "dmso"]
    real(wp), parameter :: ref_energies(10) = &
-      &[-30.376518115875_wp,-24.102578449616_wp,-23.754139493763_wp, &
-      & -22.766727017808_wp,-27.757889554228_wp,-18.587445483567_wp, &
-      & -33.445663939387_wp,-30.003461899598_wp,-20.573488191967_wp, &
-      & -25.670456523922_wp]
+      &[-30.398257570644_wp,-24.125868305041_wp,-23.787177902522_wp, &
+      & -22.779539008049_wp,-27.783054701847_wp,-18.610486346192_wp, &
+      & -33.456896298026_wp,-30.008556230192_wp,-20.588957648989_wp, &
+      & -25.684670492104_wp]
    real(wp), parameter :: ref_gnorms(10) = &
-      &[0.065115699688_wp, 0.057742250527_wp, 0.041885898146_wp, &
-      & 0.072134973561_wp, 0.048230827198_wp, 0.052250268149_wp, &
-      & 0.045597725657_wp, 0.062065139853_wp, 0.054691676440_wp, &
-      & 0.045829509846_wp]
+      &[0.070117675966_wp, 0.060272066809_wp, 0.048063628868_wp, &
+      & 0.076296084561_wp, 0.050041916284_wp, 0.051542825738_wp, &
+      & 0.046066119467_wp, 0.060436009320_wp, 0.058023381592_wp, &
+      & 0.050440402702_wp]
    real(wp), parameter :: ref_hlgaps(10) = &
-      &[2.608938030439_wp, 1.390465293950_wp, 0.169294532274_wp, &
-      & 1.254915268362_wp, 2.137937542332_wp, 2.267712835326_wp, &
-      & 2.669493177775_wp, 0.840230142925_wp, 3.341412667263_wp, &
-      & 0.393537743933_wp]
+      &[3.173028297842_wp, 1.553006040621_wp, 0.324761161079_wp, &
+      & 1.233091187215_wp, 1.918282889245_wp, 2.067664999523_wp, &
+      & 2.757505697757_wp, 0.846361565116_wp, 3.336544801399_wp, &
+      & 0.315118656281_wp]
 
    call init(env)
-   do iMol = 1, 2
+   do iMol = 1, 10
 
       call getMolecule(mol, mindless(iMol))