Example: XCDFT: Charge Separation of an ethylene dimer¶
Download XCDFT_FDE_ET_ethylene.run
#!/bin/sh
# ==============================================================================================
#
# Charge Separation Calculation of a ethylene dimer:
# C2H4* + C2H4 --> C2H4+ + C2H4-
# aimed at:
#
# 1) calculate site energies and couplings of fde-derived of a localized exciton
# (Diabat 1) and charge-separated state (Diabat 2). The exciton is obtained by using
# XCDFT method.
#
# 2) calculate the charge-transfer excitation energy from a two-state model that
# includes the two charge-localized states involved in the calculation
#
# First the isolated (restricted) neutral fragments are obtained. Symmetry NOSYM is used.
# In addition, an isolated unrestricted neutral calculation of the fragment to be excited is performed.
# Resulting files: t21.iso.rho1, t21.iso.rho2 and gs.t21. Next in the first FDE calculation:
# state C2H4* (neutral-XCDFT excitation) and C2H4(neutral), resulting files:
# fragA1.t21 and fragA2.t21. The freeze and thaw cycles are done manually since
# open-shell fragments were used. Next in the second FDE calculation: state C2H4+ and C2H4-,
# resulting files fragB1.t21 and fragB2.t21. Again freeze and thaw cycles are done manually since
# open-shell fragments were used.
#
# In the final charge separation calculation the ELECTRONTRANSFER block keyword is used.
# The files fragA1.t21, fragA2.t21, fragB1.t21, and fragB2.t21 must exist and must have these names.
# ===================================================================================================
# ==================================================
# OBTAIN ISOLATED FRAGMENTS
# ==================================================
$ADFBIN/adf << eor
Title MODCO: Fragment no. 1; (isolated)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
ATOMS
H 0.930241 1.239503 0.000000
H -0.930241 1.239503 0.000000
C 0.000000 0.667450 0.000000
C 0.000000 -0.667450 0.000000
H 0.930241 -1.239503 0.000000
H -0.930241 -1.239503 0.000000
END
BASIS
Type TZP
Core None
END
eor
rm logfile
mv TAPE21 t21.iso.rho1
$ADFBIN/adf << eor
Title MODCO: Fragment no. 2; (isolated)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
ATOMS
H 0.930241 1.239503 8.000000
H -0.930241 1.239503 8.000000
C 0.000000 0.667450 8.000000
C 0.000000 -0.667450 8.000000
H 0.930241 -1.239503 8.000000
H -0.930241 -1.239503 8.000000
END
BASIS
Type TZP
Core None
END
eor
rm logfile
mv TAPE21 t21.iso.rho2
# ==================================================
# OBTAIN ISOLATED UNRESTRICTED FRAGMENT
# ==================================================
$ADFBIN/adf << eor
Title Fragment 1; (isolated_unrestricted)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
CHARGE 0 0
UNRESTRICTED
ATOMS
H 0.930241 1.239503 0.000000
H -0.930241 1.239503 0.000000
C 0.000000 0.667450 0.000000
C 0.000000 -0.667450 0.000000
H 0.930241 -1.239503 0.000000
H -0.930241 -1.239503 0.000000
END
BASIS
Type TZP
Core None
END
eor
rm logfile
# ==================================================
# RENAME TAPE21 file as gs.t21, as required in
# XCDFT methodology.
# ==================================================
mv TAPE21 gs.t21
# ==================================================
# FIRST FDE CALCULATION: STATE D* (XCDFT) + A
# note: the freeze and thaw is done manually
# as we have open-shell fragments
# ==================================================
$ADFBIN/adf << eor
Title MODCO: Fragment no. 1; (polarized)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
CDFT
MAXITER 250
NCONSTRAINTS 1
EXCITEDCDFT
METRIC
ALLATOMS
NATOMSPERSET 36
CONSTRAINTS 1.0
INITIALMULTIPLIERS 0.0
THRESHOLD 1.0e-9
STEPSIZE 0.4
PRINT LOW
END
CHARGE 0 0
UNRESTRICTED
FRAGMENTS
rho1 t21.iso.rho1
rho2 t21.iso.rho2 type=fde
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
END
eor
rm logfile
mv TAPE21 t21.emb.rho1
$ADFBIN/adf << eor
Title MODCO: Fragment no. 2; (polarized)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
CHARGE 0 0
UNRESTRICTED
FRAGMENTS
rho1 t21.emb.rho1 subfrag=active type=fde
rho2 t21.iso.rho2
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
END
eor
rm logfile
mv TAPE21 t21.emb.rho2
it=1
while [ $it -le 2 ]; do
$ADFBIN/adf << eor
Title MODCO: Fragment no. 1; relaxed
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
NumericalQuality Good
CDFT
MAXITER 250
NCONSTRAINTS 1
EXCITEDCDFT
METRIC
ALLATOMS
NATOMSPERSET 36
CONSTRAINTS 1.0
INITIALMULTIPLIERS 0.0
THRESHOLD 1.0e-9
STEPSIZE 0.4
PRINT LOW
END
CHARGE 0 0
UNRESTRICTED
FRAGMENTS
rho1 t21.iso.rho1
rho2 t21.emb.rho2 subfrag=active type=fde
END
restart
file t21.emb.rho1
end
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
FullGrid
Energy
END
eor
rm logfile
mv TAPE21 t21.emb.rho1
$ADFBIN/adf << eor
Title MODCO: Fragment no. 2; relaxed
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
NumericalQuality Good
restart
file t21.emb.rho2
end
CHARGE 0 0
UNRESTRICTED
FRAGMENTS
rho1 t21.emb.rho1 subfrag=active type=fde
rho2 t21.iso.rho2
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
FullGrid
Energy
END
eor
rm logfile
mv TAPE21 t21.emb.rho2
it=$(($it+1))
done
# ======================================
# 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 fragA1.t21
mv t21.emb.rho2 fragA2.t21
# ==================================================
# SECOND FDE CALCULATION: STATE D+ + A-
# note: the freeze and thaw is done manually
# as we have open-shell fragments
# ==================================================
$ADFBIN/adf << eor
Title MODCO: Fragment no. 1; (polarized)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
CHARGE 1 -1
UNRESTRICTED
FRAGMENTS
rho1 t21.iso.rho1
rho2 t21.iso.rho2 type=fde
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
END
eor
rm logfile
mv TAPE21 t21.emb.rho1
$ADFBIN/adf << eor
Title MODCO: Fragment no. 2; (polarized)
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
CHARGE -1 1
UNRESTRICTED
FRAGMENTS
rho1 t21.emb.rho1 subfrag=active type=fde
rho2 t21.iso.rho2
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
END
eor
rm logfile
mv TAPE21 t21.emb.rho2
it=1
while [ $it -le 2 ]; do
$ADFBIN/adf << eor
Title MODCO: Fragment no. 1; relaxed
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
NumericalQuality Good
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
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
FullGrid
Energy
END
eor
rm logfile
mv TAPE21 t21.emb.rho1
$ADFBIN/adf << eor
Title MODCO: Fragment no. 2; relaxed
EPRINT
SFO NOEIG NOOVL NOORBPOP
END
NOPRINT BAS FUNCTIONS
SYMMETRY NOSYM
XC
model SAOP
END
NumericalQuality Good
restart
file t21.emb.rho2
end
CHARGE -1 1
UNRESTRICTED
FRAGMENTS
rho1 t21.emb.rho1 subfrag=active type=fde
rho2 t21.iso.rho2
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
ALLOW PARTIALSUPERFRAGS
FDE
PW91K
GGAPOTXFD pw91x
GGAPOTCFD pw91c
FullGrid
Energy
END
eor
rm logfile
mv TAPE21 t21.emb.rho2
it=$(($it+1))
done
# ======================================
# 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) hybrids not supported
# 3) NumericalQuality GOOD is needed for accuracy
# ======================================
$ADFBIN/adf << eor
Title ET calculation at R=0.0 Angstrom
EPRINT
SFO NOEIG NOOVL NOORBPOP
SCF NOPOP
END
NOPRINT BAS FUNCTIONS
FRAGMENTS
rho1 t21.iso.rho1
rho2 t21.iso.rho2
END
ATOMS
H 0.930241 1.239503 0.000000 f=rho1
H -0.930241 1.239503 0.000000 f=rho1
C 0.000000 0.667450 0.000000 f=rho1
C 0.000000 -0.667450 0.000000 f=rho1
H 0.930241 -1.239503 0.000000 f=rho1
H -0.930241 -1.239503 0.000000 f=rho1
H 0.930241 1.239503 8.000000 f=rho2
H -0.930241 1.239503 8.000000 f=rho2
C 0.000000 0.667450 8.000000 f=rho2
C 0.000000 -0.667450 8.000000 f=rho2
H 0.930241 -1.239503 8.000000 f=rho2
H -0.930241 -1.239503 8.000000 f=rho2
END
NumericalQuality Good
UNRESTRICTED
CHARGE 0 0
XC
GGA PW91
END
SYMMETRY nosym
SCF
iterations 0
END
Beckegrid
Quality Good
END
ELECTRONTRANSFER
numfrag 2
END
eor
rm logfile