Example: FDE NMR spin-spin coupling: NH3-H2O¶

#! /bin/sh

# This example demonstrates calculation of NMR spin-spin couplings (J coupling)
# in case of frozen density embedding (FDE). It performs single point runs for
# H2O and NH3 with PBE/(ZORA/jcpl basis) (all-electron) and uses these fragments
# in:
# - an FDE embedding calculation calculation in which water in presence of a
#   frozen ammonia is computed (first the electron density / KS orbitals with 
#   ADF then the NMR J couplings with CPL (scalar code branch))
# - a corresponding FDE freeze-thaw calculation followed by calculation of NMR J
#   couplings with CPL scalar, then spin-orbit code branch

# First NH3 with PBE and an all electron TZP basis set. No cpl calculation for
# NH3, thus regular basis is OK. This is not shown. Next H2O with PBE and an all
# electron ZORA/jcpl basis set:

# NH3 PBE/TZP (no cpl calculation for NH3, thus regular basis is OK)

AMS_JOBNAME=NH3 $AMSBIN/ams <<eor
System
  atoms
     N       -1.39559       -0.02156        0.00004
     H       -1.62981        0.96110       -0.10622
     H       -1.86277       -0.51254       -0.75597
     H       -1.83355       -0.33077        0.86231
  end
end

Task SinglePoint

Engine ADF
  title NH3 PBE/TZP single point
  eprint
    scf NOPOP
    sfo NOEIG NOOVL NOORBPOP
  end
  exactdensity
  basis
    core None
    type TZP
  end
  noprint BAS FUNCTIONS
  numericalquality Good
  symmetry NOSYM
  xc
    gga PBE
  end
  Relativity Level=None
EndEngine
eor

mv NH3.results/adf.rkf t21.ammonia


# H2O PBE/(ZORA/jcpl)


AMS_JOBNAME=H2O $AMSBIN/ams <<eor
System
  atoms
     O        1.56850        0.10589        0.00001
     H        0.60674       -0.03396       -0.00063
     H        1.94052       -0.78000        0.00022
  end
end

Task SinglePoint

Engine ADF
  eprint
    scf NOPOP
    sfo NOEIG NOOVL NOORBPOP
  end
  exactdensity
  basis
    core None
    type ZORA/jcpl
  end
  noprint BAS FUNCTIONS
  numericalquality Good
  symmetry NOSYM
  title H2O PBE/(ZORA/jcpl) single point
  xc
    gga PBE
  end
  Relativity Level=None
EndEngine

eor
mv H2O.results/adf.rkf t21.water


# NH3-H2O: FDE calculation of H2O in presence of frozen NH3


AMS_JOBNAME=FDE $AMSBIN/ams <<eor
System
  atoms
     O        1.56850        0.10589        0.00001    adf.f=frag1
     H        0.60674       -0.03396       -0.00063    adf.f=frag1
     H        1.94052       -0.78000        0.00022    adf.f=frag1
     N       -1.39559       -0.02156        0.00004    adf.f=frag2
     H       -1.62981        0.96110       -0.10622    adf.f=frag2
     H       -1.86277       -0.51254       -0.75597    adf.f=frag2
     H       -1.83355       -0.33077        0.86231    adf.f=frag2
  end
end

Task SinglePoint

Engine ADF
  eprint
    scf NOPOP
    sfo NOEIG NOOVL NOORBPOP
  end
  exactdensity
  fde
    pw91k
  end
  fragments
     frag1  t21.water
     frag2  t21.ammonia type=FDE
  end
  noprint BAS FUNCTIONS
  numericalquality Good
  save TAPE10
  symmetry NOSYM
  title NH3-H2O PBE/PW91k/(ZORA/jcpl) FDE single point calculation (no freeze-thaw)
  xc
    gga PBE
  end
  Relativity Level=None
EndEngine
eor


# NH3-H2O CPL calculation J(O-H) in water H-bond donor


"$AMSBIN/cpl" <<eor
 tape10file FDE.results/TAPE10
 adffile FDE.results/adf.rkf
 GGA
 NMRCoupling
  fc
  dso
  pso 
  AtomPert 1
  AtomResp 2
  scf iterations=15 converge=1.0e-05
 End
eor
rm TAPE21 TAPE10 logfile


# NH3-H2O FDE calculation (1 freeze-thaw cycle)


AMS_JOBNAME=FDE1 $AMSBIN/ams <<eor
System
  atoms
     O        1.56850        0.10589        0.00001    adf.f=frag1
     H        0.60674       -0.03396       -0.00063    adf.f=frag1
     H        1.94052       -0.78000        0.00022    adf.f=frag1
     N       -1.39559       -0.02156        0.00004    adf.f=frag2
     H       -1.62981        0.96110       -0.10622    adf.f=frag2
     H       -1.86277       -0.51254       -0.75597    adf.f=frag2
     H       -1.83355       -0.33077        0.86231    adf.f=frag2
  end
end

Task SinglePoint

Engine ADF
  eprint
    scf NOPOP
    sfo NOEIG NOOVL NOORBPOP
  end
  exactdensity
  fde
    pw91k
    relaxcycles 1
  end
  fragments
     frag1  t21.water
     frag2  t21.ammonia type=FDE  &
     fdeoptions RELAX
     SubEnd
  end
  noprint BAS FUNCTIONS
  numericalquality Good
  save TAPE10
  symmetry NOSYM
  title NH3-H2O PBE/PW91k/(ZORA/jcpl) FDE single point calculation (1 freeze-thaw cycle)
  xc
    gga PBE
  end
  Relativity Level=None
EndEngine
eor


# NH3-H2O CPL calculation J(O-H) in water H-bond donor
# tests scalar code branch (no sd term)


"$AMSBIN/cpl" <<eor
 tape10file FDE1.results/TAPE10
 adffile FDE1.results/adf.rkf
 GGA
 NMRCoupling
  fc
  dso
  pso 
  AtomPert 1
  AtomResp 2
  scf iterations=15 converge=1.0e-05
 End
eor
rm logfile


# NH3-H2O CPL calculation J(O-H) in water H-bond donor
# tests spin-orbit code branch (sd term)


"$AMSBIN/cpl" <<eor
 tape10file FDE1.results/TAPE10
 adffile FDE1.results/adf.rkf
 GGA
 NMRCoupling
  fc
  sd
  dso
  pso 
  AtomPert 1
  AtomResp 2
  scf iterations=15 converge=1.0e-05
 End
eor
rm t21.H t21.N t21.O t21.water t21.ammonia