TURBOMOLE Users Forum
Forum General => Miscellaneous => Topic started by: marilu98 on November 13, 2023, 10:36:59 AM
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Dear all,
I'm computing ground state energies at B3LYP/6-31+G* (defining manually the basis file) and for some of my systems the SCF (within dscf module) do not converge and gives really deep energies (of the order of -10^6 hartree).
I'm quite sure about the basis specified since it works for other "similar" systems.
I tried to modify $scforbitalshift, $scfdamp, gridsize, type of guess, but without success. I'd like to try to modify the threshold for basis linear dependencies and the threshold for neglecting one electron integral. Do you know if there are some keywords to do the latter within dscf module ?
Did any of you encounter this type of problems ?
I thank you all in advance.
Best regards
Marilu
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Hello,
my guess would be that the functional is causing those numerical errors, this can happen if the basis set generates some really unusual density and density derivatives at certain points.
Does the same input run with a predefined basis set (not a manually modified one)?
Best Regards
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Thank you for your reply.
I don't think that is a problem of the functional (I tried also other xcf like tpssh and pbe0).
With aug-cc-pVDZ I have no problems, as well as with bs (external or built in) without diffuse functions (6-31G*, 3-21G*, cc-pVDZ,...).
The problem is that B3LYP/6-31+G* level is not working for some of my systems (namely 12 out of 48), so it is not a systematic error. My guess it's that for these systems linear dependencies are more crucial....thus, I'd like to remove some of them (if it is possible).
Thank you once again
Best regards
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Hi,
is the input structure prone to linear dependencies of the basis set if diffuse functions are used? Like a fullerene where all diffuse functions 'flood' the inner part of the fullerene?
As far as I can see aug-cc-pVDZ is not less diffuse than 6-31+G* (I just downloaded both basis sets for carbon from https://www.basissetexchange.org/ and compared them).
Is it possible to post the structure of one of those cases (coord file and also the basis set file you have used)?
Best Regards
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Hi,
thank you very much once again. In fact, I have problems with systems that contain triple CC bonds.
Here an example (it is from the paper J. Chem. Theory Comput. 2022, 18, 2, 1046–1060):
$coord
9.27006233815159 -4.56563200912835 0.00013379544421 h
4.64141236904137 -4.32483962923246 0.00013182805034 h
5.05918122897159 3.75748513925418 -0.00010634112513 h
9.66505382813530 3.54143798936859 -0.00010887127944 h
-3.67501791919848 -3.89309077933371 -0.00010509711842 h
-3.25648850932071 4.19556853915043 0.00011925041120 h
-8.32979991840199 -3.64789074931242 -0.00010594314881 h
-7.93772671848856 4.41415218923358 0.00011623176269 h
-15.81144469698963 -0.50727138483899 -1.67389502958465 h
-15.75527819702021 -3.44057121940902 -0.00010840943037 h
-15.81145089699207 -0.50737682191914 1.67386171976020 h
16.41873589675920 2.04080322952146 -0.00006053284106 h
13.80513209730624 3.27359241934086 -1.68893740959647 h
13.80512039725591 3.27368692926867 1.68873124973594 h
8.35084343836196 -2.73888994941181 0.00007836070629 c
5.74629668879938 -2.60666967941831 0.00007860126843 c
4.49886966908027 -0.26110449798891 0.00001062063877 c
5.97959980891925 1.93352382967140 -0.00005539221908 c
8.59585792826932 1.80436951956161 -0.00005627037481 c
9.81767446813259 -0.53413285394070 0.00001026385847 c
1.82241367963363 -0.12226715902900 0.00000922356424 c
-0.45911807593796 -0.00608386365412 0.00000770327957 c
-3.13570901941989 0.13323481802946 0.00000705000125 c
-4.60739961919282 -2.07607416960626 -0.00005649241763 c
-4.37115621920461 2.48437982950287 0.00006990720545 c
-7.21746430856807 -1.93788686959910 -0.00005681008059 c
-6.97894704856623 2.61135661953761 0.00006833816584 c
-8.43051093826820 0.40687496393239 0.00000522736041 c
-11.22667899787731 0.66458740692910 0.00000708666194 c
-15.12622359708390 -1.48762030975725 -0.00004640146910 c
14.37355899722264 2.24752188963408 -0.00007215975899 c
-12.34226999752111 2.65789218946130 0.00005136653552 o
-12.41664749751367 -1.59239539976045 -0.00004424018933 o
13.13702549744587 -0.95154658274258 0.00001396280839 s
$end
I agree with you: 6-31+G* has less diffuse functions with respect to aug-cc-pVDZ... this is why I can't spot properly the problem.
The only difference is that aug-cc-pVDZ is implemented and I used 6-31+G* as implemented in QChem.
Best regards
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I'm now trying the same calculation with HF (to have a better guess to feed a DFT calculation) and I still have extremely oscillating scf energies. Hereafter some cycles:
ITERATION ENERGY 1e-ENERGY 2e-ENERGY NORM[dD(SAO)] TOL
2 -975974.79994451 -4311.6171875 -973025.53918 0.467D+11 0.102D-11
Norm of current diis error: 4.4348
max. resid. norm for Fia-block= 1.448D+05 for orbital 25a
max. resid. fock norm = 1.454D+05 for orbital 25a
Delta Eig. = **************** eV
current damping : 0.850
ITERATION ENERGY 1e-ENERGY 2e-ENERGY NORM[dD(SAO)] TOL
3 -1019817.0084406 -4249.1926270 -1016930.1722 0.584D+09 0.102D-11
Norm of current diis error: 5.1341
max. resid. norm for Fia-block= 4.385D+01 for orbital 1a
max. resid. fock norm = 3.580D+02 for orbital 1a
Delta Eig. = **************** eV
current damping : 0.900
ITERATION ENERGY 1e-ENERGY 2e-ENERGY NORM[dD(SAO)] TOL
4 -1019817.9718195 -4261.4228516 -1016918.9054 0.251D+05 0.102D-11
Norm of current diis error: 2.9852
max. resid. norm for Fia-block= 7.470D+01 for orbital 1a
max. resid. fock norm = 6.127D+02 for orbital 1a
Delta Eig. = **************** eV
current damping : 0.950
ITERATION ENERGY 1e-ENERGY 2e-ENERGY NORM[dD(SAO)] TOL
5 92468.401837716 -4271.7119141 95377.757324 0.251D+05 0.809D-11
Norm of current diis error: 1.5651
max. resid. norm for Fia-block= 3.087D+03 for orbital 1a
max. resid. fock norm = 1.669D+04 for orbital 1a
mo-orthogonalization: Cholesky decomposition
Delta Eig. = **************** eV
Note the positive energy of iteration 5.
Hereafter my control file generated using define:
$title
$symmetry c1
$user-defined bonds file=coord
$coord file=coord
$optimize
internal off
redundant off
cartesian on
global off
basis off
$atoms
h 1-14 \
basis =h 6-31+G*
c 15-31 \
basis =c 6-31+G*
o 32-33 \
basis =o 6-31+G*
s 34 \
basis =s 6-31+G*
$basis file=basis
$scfmo scfdump=30 format(4d20.14)
$scfiterlimit 100
$scfconv 7
$thize 0.10000000E-04
$thime 5
$scfdamp start=1.000 step=0.050 min=0.100
$scfdump
$scfintunit
unit=30 size=0 file=twoint
$scfdiis
$maxcor 500 MiB per_core
$scforbitalshift closedshell=.4
$drvopt
cartesian on
basis off
global off
hessian on
dipole on
nuclear polarizability
$interconversion off
qconv=1.d-7
maxiter=25
$coordinateupdate
dqmax=0.3
interpolate on
statistics 5
$forceupdate
ahlrichs numgeo=0 mingeo=3 maxgeo=4 modus=<g|dq> dynamic fail=0.3
threig=0.005 reseig=0.005 thrbig=3.0 scale=1.00 damping=0.0
$forceinit on
diag=default
$end
The basis file contains the external basis set.
I'm using Turbomole7.6
I have two questions:
1) is there any way to do basis set projection (i.e. use a smaller basis set first and the use the basis set needed).
2) I cannot impose hcore guess. By following the manual (i.e. using $scfmo none) I still have a EHT starting vectors in the output. Do you have any experience with this? (dscf module)
Thank you to everybody in advance.
Best regards,
Marilu
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Hi,
what did help for me was to
- use RI-DFT
- set $scftol 1d-15 as I described here: https://forum.turbomole.org/index.php/topic,401.0.html
With Turbomole 7.7 (should also work with 7.6 but probably not older versions), I used this simple control file as input:
$coord file=coord
$scftol 1d-15
$basis file=basis
$symmetry c1
$atoms
basis = 6-31+G*
jbas = universal
$dft
functional b3-lyp
$rij
$marij
$end
coord file contained your coordinates and basis file was what I have downloaded from https://www.basissetexchange.org/ .
Attached the input and the output of ridft. It converged in 15 SCF iterations.
I do not think that DFT is causing problems here as Hartree-Fock shows the same behavior.
The geometry has almost Cs symmetry, and if you enforce Cs (call define and in the geometry menu 'desy 0.1', this will find Cs and also moves the coordinates to the exact positions of the symmetric structure), the calculation also runs fine without the need to set any keywords like $scftol.
Using other diffuse basis sets like def2-SVPD or aug-cc-pVDZ might be the better option.
Best Regards