Example: Charge transfer integrals with FDE: water dimer

Download ElectronTransfer_FDE_H2O.run

#!/bin/sh

# == Expert Option ==

# The electron transfer calculation of a water dimer radical cation in this
# example is aimed at:

# - calculate site energies and couplings of FDE-derived charge-localized states
# - calculate the charge-transfer excitation energy from a two-state model that
#   includes the two charge-localized states involved in the calculation
# - the output also includes a rough evaluation of the error introduced by the
#   density fitting on the site energies and coupling


# First the isolated neutral fragments are obtained. Symmetry NOSYM is used.
# Next in the first FDE calculation the localized state D+A is calculated, which
# means that the first water molecule has charge +1, and the second water
# molecule is neutral. The resulting TAPE21 files must be renamed to fragA1.t21
# and fragA2.t21. In the second FDE calculation the localized state DA+ is
# calculated, now the second water molecule has charge +1, and the first water
# molecule is neutral. The resulting TAPE21 files must be renamed to fragB1.t21
# and fragB2.t21. The FDE freeze and thaw cycle is done manually, and a spin-
# unrestricted calculation is performed.

# The electron transfer calculation is next. The files fragA1.t21, fragA2.t21,
# fragB1.t21, and fragB2.t21 must exist and must have these names. The program
# must be execute in serial mode. Hybrids are not supported. An integration
# parameter of 6 is needed for accuracy.


# == The output of this example is discussed here ==


# ============  Electron Transfer RESULTS ===================

# Electronic Coupling =         0.000000 eV
# Electronic Coupling =        -0.000006 cm-1
# H11-H22             =        -1.396836 eV
# Excitation Energy   =         1.396836 eV
# Overlap             =         0.000000
# H11 H22 H12 =  -152.443044906236  -152.391712133030  -151.743951196449 Eh
# S11 S22 S12 =     0.981761438554     0.980941502465    -0.000000000038


# =========== END Electron Transfer RESULTS ================

# Due to symmetry, the overlap is almost diagonal (Overlap = 0.00), thus the
# transition density is evaluated with one less electron as explained in Ref.
# [353] in the ADF Manual.

# The electronic coupling between the state with a positive charge localized on
# one water molecule and another with the charge localized on the other water
# molecule is given by 'Electronic Coupling' and is reported in eV and cm^-1.

# 'H11-H22' is the difference of the site energies in eV. Values of the site
# energies are given by the first two values of 'H11 H22 H12' in atomic units.

# 'Excitation Energy' reports the value of the transfer excitation energy as
# calculated by diagonalization of the 2X2 generalized eigenvalue problem in
# the basis of the charge-localized states, see Refs.[352,353] in the ADF
# Manual.

# 'S11 S22 S12' are the values of the non-normalized overlaps.


# ==================================================
#           OBTAIN ISOLATED FRAGMENTS
# ==================================================


$ADFBIN/adf -n 1  <<eor
Title Isolated water molecule 1

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000  
H        -0.9358409558         .2646136961      0.0000000000           
H        -0.0304663436       -0.9828924420      0.0000000000           
END

NumericalQuality good

BASIS
 Type TZP 
 Core None
END

eor

mv TAPE21 t21.iso.rho1

$ADFBIN/adf -n 1  <<eor
Title isolated water molecule 2

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

ATOMS
 O         0.0000000000       -2.9053396088        0.0000000000  
 H        -0.4092227596       -3.3374838250       -0.7701260000  
 H        -0.4092227596       -3.3374838250        0.7701260000  
END

NumericalQuality good

BASIS
 Type TZP 
 Core None
END

eor

mv TAPE21 t21.iso.rho2

# ==================================================
#   FIRST FDE CALCULATION: STATE D+A
#   note: the freeze and thaw is done manually
#         as we have open-shell fragments
# ==================================================


$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          1; (polarized)

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

CHARGE 1 1
UNRESTRICTED

FRAGMENTS
  rho1 t21.iso.rho1 
  rho2 t21.iso.rho2 type=fde
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho1

$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          2; (polarized)

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91
END

SCF
  iterations 90
END

FRAGMENTS
  rho1 t21.emb.rho1 subfrag=active type=fde
  rho2 t21.iso.rho2 
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho2


$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          1; relaxed

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

CHARGE 1 1
UNRESTRICTED

FRAGMENTS
  rho1 t21.iso.rho1 
  rho2 t21.emb.rho2 subfrag=active type=fde
END

restart 
  File t21.emb.rho1
End

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho1

$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          2; relaxed

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

FRAGMENTS
  rho1 t21.emb.rho1 subfrag=active type=fde
  rho2 t21.emb.rho2 subfrag=active 
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho2

mv t21.emb.rho1 fragA1.t21
mv t21.emb.rho2 fragA2.t21


# ==================================================
#   SECOND FDE CALCULATION: STATE DA+
#   note: the freeze and thaw is done manually
#         as we have open-shell fragments
#   note: now rho1 is the second fragment 
#         as rho2 is the cation
# ==================================================


$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          2; (polarized)

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91
END

SCF
  iterations 90
END

CHARGE 1 1
UNRESTRICTED

FRAGMENTS
  rho1 t21.iso.rho1 type=fde
  rho2 t21.iso.rho2 
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho2


$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          1; (polarized)

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

FRAGMENTS
  rho1 t21.iso.rho1 
  rho2 t21.emb.rho2 subfrag=active type=fde
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho1

$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          2; relaxed

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

CHARGE 1 1
UNRESTRICTED

restart 
  File t21.emb.rho2
End

FRAGMENTS
  rho1 t21.emb.rho1 subfrag=active type=fde
  rho2 t21.iso.rho2 
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho2

$ADFBIN/adf -n 1 <<eor
Title MODCO: Fragment no.          1; relaxed

EPRINT
  SFO NOEIG NOOVL NOORBPOP
END

NOPRINT BAS FUNCTIONS


SYMMETRY NOSYM

XC
  GGA PW91 
END

SCF
  iterations 90
END

FRAGMENTS
  rho1 t21.emb.rho1 subfrag=active 
  rho2 t21.emb.rho2 subfrag=active type=fde
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END

NumericalQuality good

ALLOW PARTIALSUPERFRAGS

FDE
  PW91K
  GGAPOTXFD pw91x
  GGAPOTCFD pw91c
END

eor

mv TAPE21 t21.emb.rho1

# ======================================
# NOW THE TAPE21 FILES MUST BE RENAMED
# 
#  TO: fragA1.t21, fragA2.t21 
#      .... up to a max of fragA999.t21
# AND: fragB1.t21, fragB2.t21 
#      .... up to a max of fragB999.t21 
# ======================================

mv t21.emb.rho1 fragB1.t21
mv t21.emb.rho2 fragB2.t21

# ======================================
# Electron Transfer calculation is next
#
# 1) note the ELECTRONTRANSFER block keyword
# 2) the program must be execute in 
#    serial mode (parallel mode not 
#    supported)
# 3) hybrids not supported
# 4) an integration parameter of 6 is 
#    needed for accuracy
# ======================================

$ADFBIN/adf -n 1 <<eor
Title ElectronTransfer calculation 

EPRINT
  SFO NOEIG NOOVL NOORBPOP
  SCF NOPOP
END

NOPRINT BAS FUNCTIONS


FRAGMENTS
 rho1 t21.iso.rho1 
 rho2 t21.iso.rho2 
END

ATOMS
O         0.0000000000        0.0000000000      0.0000000000   f=rho1
H        -0.9358409558         .2646136961      0.0000000000   f=rho1
H        -0.0304663436       -0.9828924420      0.0000000000   f=rho1
O         0.0000000000       -2.9053396088      0.0000000000   f=rho2
H        -0.4092227596       -3.3374838250     -0.7701260000   f=rho2
H        -0.4092227596       -3.3374838250      0.7701260000   f=rho2
END                                                   

NumericalQuality good
                                                      
CHARGE 1 1                                            
UNRESTRICTED                                          

XC
  GGA PW91
END

SYMMETRY nosym

SCF
  iterations 0
END

ELECTRONTRANSFER
 numfrag 2
END

eor