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Jakub
Apr 26, 2022, 5:55:03 PM4/26/22
to NWChem Forum
Hi all,
I'm trying to perform a coupling calculation using the ET module using an output of CDFT calculations. I'm interested in a triplet-triplet transfer between two anthracenes.
The first step is to find the localised triplet states using CDFT. And while the first cdft calculation (with the triplet localised on the 'donor') works fine, the second one (which should be equivalent) fails with the "CDFT: multipliers go over limit " error. The input is attached below. Any idea how to fix this? Thanks!
(I'm using NWChem 7.0.0)
___________________________
echo
MEMORY STACK 1500 mb HEAP 150 mb GLOBAL 1800 mb noverify
start anthracene
title "Title"
charge 0
geometry da units angstroms print xyz
C 8.46805 -15.49835 -0.29888
C 7.04311 -15.49835 -0.29888
C 6.35033 -14.31954 -0.29888
C 7.03407 -13.06458 -0.29888
C 9.16082 -14.31954 -0.29888
C 8.47709 -13.06458 -0.29888
C 6.35354 -11.84255 -0.29888
C 7.03407 -10.62051 -0.29888
C 9.15761 -11.84255 -0.29888
C 8.47709 -10.62051 -0.29888
C 6.35033 -9.36556 -0.29888
C 7.04311 -8.18674 -0.29888
C 8.46805 -8.18674 -0.29888
C 9.16082 -9.36556 -0.29888
H 9.00052 -16.44262 -0.29888
H 6.51064 -16.44262 -0.29888
H 5.26534 -14.31901 -0.29888
H 10.24582 -14.31901 -0.29888
H 5.26769 -11.84255 -0.29888
H 10.24346 -11.84255 -0.29888
H 5.26534 -9.36609 -0.29888
H 6.51064 -7.24247 -0.29888
H 9.00052 -7.24247 -0.29888
H 10.24582 -9.36609 -0.29888
C 4.42418 -14.27653 10.00050
C 5.82796 -14.23446 9.75913
C 3.69581 -13.12073 10.05538
H 7.53318 -13.00523 9.39555
H 3.93654 -15.23450 10.14070
H 2.53260 -10.68106 10.10755
H 2.62694 -13.15226 10.23913
H 2.43372 -8.20999 9.97674
H 7.33996 -8.06296 9.13316
H 7.43430 -10.53417 9.26474
H 6.03036 -5.98073 9.23159
H 6.38927 -15.16100 9.71898
H 3.57763 -6.05423 9.65331
C 5.74188 -11.80567 9.62867
C 3.60233 -10.64900 9.92362
C 6.46436 -13.03776 9.57935
C 4.32037 -11.84826 9.87309
C 6.27109 -8.09450 9.31691
C 5.54272 -6.93870 9.37179
C 4.13894 -6.98077 9.61316
C 4.22502 -9.40956 9.74362
C 6.36457 -10.56622 9.44867
C 5.64653 -9.36696 9.49920
C 3.50254 -8.17746 9.79294
end
basis
* library 6-31G*
end
#----------------------------------------------------------------------------------
set geometry da
charge 0
dft
direct
mult 3
odft
XC b3lyp
maxiter 500
cdft 1 24 charge 0
cdft 1 24 spin 2
cdft 25 48 charge 0
cdft 25 48 spin 0
vectors output reactant.movecs
convergence nolevelshifting
end
set dft:cdft_maxiter 1000
task dft
#----------------------------------------------------------------------------------
set geometry da
charge 0
dft
direct
mult 3
odft
XC b3lyp
maxiter 500
cdft 1 24 charge 0
cdft 1 24 spin 0
cdft 25 48 charge 0
cdft 25 48 spin 2
vectors output product.movecs
convergence nolevelshifting
end
set dft:cdft_maxiter 1000
task dft
#----------------------------------------------------------------------------------
charge 0
set geometry da
scf
uhf
singlet
vectors input reactant.movecs output reactant-scf.movecs
direct
noscf
end
task scf
#----------------------------------------------------------------------------------
charge 0
set geometry da
scf
uhf
triplet
vectors input product.movecs output product-scf.movecs
direct
noscf
end
task scf
#-----------------------------------------------------------------------------------
set geometry da
charge 0
et
vectors reactants reactant-scf.movecs
vectors products product-scf.movecs
end
task scf et
(I'm using NWChem 7.0.0)
___________________________
echo
MEMORY STACK 1500 mb HEAP 150 mb GLOBAL 1800 mb noverify
start anthracene
title "Title"
charge 0
geometry da units angstroms print xyz
C 8.46805 -15.49835 -0.29888
C 7.04311 -15.49835 -0.29888
C 6.35033 -14.31954 -0.29888
C 7.03407 -13.06458 -0.29888
C 9.16082 -14.31954 -0.29888
C 8.47709 -13.06458 -0.29888
C 6.35354 -11.84255 -0.29888
C 7.03407 -10.62051 -0.29888
C 9.15761 -11.84255 -0.29888
C 8.47709 -10.62051 -0.29888
C 6.35033 -9.36556 -0.29888
C 7.04311 -8.18674 -0.29888
C 8.46805 -8.18674 -0.29888
C 9.16082 -9.36556 -0.29888
H 9.00052 -16.44262 -0.29888
H 6.51064 -16.44262 -0.29888
H 5.26534 -14.31901 -0.29888
H 10.24582 -14.31901 -0.29888
H 5.26769 -11.84255 -0.29888
H 10.24346 -11.84255 -0.29888
H 5.26534 -9.36609 -0.29888
H 6.51064 -7.24247 -0.29888
H 9.00052 -7.24247 -0.29888
H 10.24582 -9.36609 -0.29888
C 4.42418 -14.27653 10.00050
C 5.82796 -14.23446 9.75913
C 3.69581 -13.12073 10.05538
H 7.53318 -13.00523 9.39555
H 3.93654 -15.23450 10.14070
H 2.53260 -10.68106 10.10755
H 2.62694 -13.15226 10.23913
H 2.43372 -8.20999 9.97674
H 7.33996 -8.06296 9.13316
H 7.43430 -10.53417 9.26474
H 6.03036 -5.98073 9.23159
H 6.38927 -15.16100 9.71898
H 3.57763 -6.05423 9.65331
C 5.74188 -11.80567 9.62867
C 3.60233 -10.64900 9.92362
C 6.46436 -13.03776 9.57935
C 4.32037 -11.84826 9.87309
C 6.27109 -8.09450 9.31691
C 5.54272 -6.93870 9.37179
C 4.13894 -6.98077 9.61316
C 4.22502 -9.40956 9.74362
C 6.36457 -10.56622 9.44867
C 5.64653 -9.36696 9.49920
C 3.50254 -8.17746 9.79294
end
basis
* library 6-31G*
end
#----------------------------------------------------------------------------------
set geometry da
charge 0
dft
direct
mult 3
odft
XC b3lyp
maxiter 500
cdft 1 24 charge 0
cdft 1 24 spin 2
cdft 25 48 charge 0
cdft 25 48 spin 0
vectors output reactant.movecs
convergence nolevelshifting
end
set dft:cdft_maxiter 1000
task dft
#----------------------------------------------------------------------------------
set geometry da
charge 0
dft
direct
mult 3
odft
XC b3lyp
maxiter 500
cdft 1 24 charge 0
cdft 1 24 spin 0
cdft 25 48 charge 0
cdft 25 48 spin 2
vectors output product.movecs
convergence nolevelshifting
end
set dft:cdft_maxiter 1000
task dft
#----------------------------------------------------------------------------------
charge 0
set geometry da
scf
uhf
singlet
vectors input reactant.movecs output reactant-scf.movecs
direct
noscf
end
task scf
#----------------------------------------------------------------------------------
charge 0
set geometry da
scf
uhf
triplet
vectors input product.movecs output product-scf.movecs
direct
noscf
end
task scf
#-----------------------------------------------------------------------------------
set geometry da
charge 0
et
vectors reactants reactant-scf.movecs
vectors products product-scf.movecs
end
task scf et
Edoardo Aprà
Apr 27, 2022, 12:43:24 PM4/27/22
to NWChem Forum
This input gets you the localized triplet states you mention without using CDFT. It uses the fragment guess https://nwchemgit.github.io/Hartree-Fock-Theory-for-Molecules.html#vectors-fragment-superposition-of-fragment-molecular-orbitals. The only tricky part is to choose a level lshifter value that converges to the desired localized triplet. I have empirically found that decreasing the level shifter value from the default 0.5 to 0.17 gets the desired solution. You can monitor the localization of the spin by examining the Spin Density Mulliken analysis.
geometry a1 units angstroms print xyz
C 8.46805 -15.49835 -0.29888
C 7.04311 -15.49835 -0.29888
C 6.35033 -14.31954 -0.29888
C 7.03407 -13.06458 -0.29888
C 9.16082 -14.31954 -0.29888
C 8.47709 -13.06458 -0.29888
C 6.35354 -11.84255 -0.29888
C 7.03407 -10.62051 -0.29888
C 9.15761 -11.84255 -0.29888
C 8.47709 -10.62051 -0.29888
C 6.35033 -9.36556 -0.29888
C 7.04311 -8.18674 -0.29888
C 8.46805 -8.18674 -0.29888
C 9.16082 -9.36556 -0.29888
H 9.00052 -16.44262 -0.29888
H 6.51064 -16.44262 -0.29888
H 5.26534 -14.31901 -0.29888
H 10.24582 -14.31901 -0.29888
H 5.26769 -11.84255 -0.29888
H 10.24346 -11.84255 -0.29888
H 5.26534 -9.36609 -0.29888
H 6.51064 -7.24247 -0.29888
H 9.00052 -7.24247 -0.29888
H 10.24582 -9.36609 -0.29888
end
geometry a2 units angstroms print xyz
geometry a2 units angstroms print xyz
basis spherical
* library 6-31G*
end
#----------------------------------------------------------------------------------
set geometry a1
charge 0
dft
sym off
adapt off
mulliken
direct
mult 1
odft
XC b3lyp
vectors input atomic output a1_singlet.mos
end
task dft
charge 0
dft
sym off
adapt off
mulliken
direct
mult 1
odft
XC b3lyp
vectors input atomic output a1_singlet.mos
end
task dft
dft
direct
mult 3
odft
XC b3lyp
vectors input a1_singlet.mos output a1_triplet.mos
end
task dft
set geometry a2
charge 0
dft
direct
mult 1
odft
XC b3lyp
vectors input atomic output a2_singlet.mos
end
task dft
end
task dft
set geometry a2
charge 0
dft
direct
mult 1
odft
XC b3lyp
vectors input atomic output a2_singlet.mos
end
task dft
dft
direct
mult 3
odft
XC b3lyp
vectors input a2_singlet output a2_triplet.mos
end
task dft
set geometry da
title "triplet on monomer 1"
dft
vectors input fragment a1_triplet.mos a2_singlet.mos output triplet_singlet.mos
convergence lshift 0.17
max_ovl
end
task dft
title "triplet on monomer 2"
dft
vectors input fragment a1_singlet.mos a2_triplet.mos output singlet_triplet.mos
end
task dft
end
task dft
set geometry da
title "triplet on monomer 1"
dft
vectors input fragment a1_triplet.mos a2_singlet.mos output triplet_singlet.mos
convergence lshift 0.17
max_ovl
end
task dft
title "triplet on monomer 2"
dft
vectors input fragment a1_singlet.mos a2_triplet.mos output singlet_triplet.mos
end
task dft
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