TDDFT Convergence Issues


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Dear NWChem Forum members,

the goal of our study is the investigation of optoelectronic properties of small clusters such as AgnCo + . Therefore we use TDDFT calculations (within the CIS approximation) based on well-established functionals and basis sets (PBE0, HSE06, LC-wPBEh and cc-pvtz, def2-tzvpp). Starting with the structures we found to be the global mininum geometry, larger clusters with n > 4 seem to fail the convercence when solving the eigenvalue problem (Davidson iteration). This issue appears to be directly related to the number of excited states nroots specified in the TDDFT block. It has been tested successfully for "nroots 60", but somehow failed for higher values (see therefore an attached input file for "nroots 80"). Instead of showing an error message in the NWChem ouptut file, the job is immediately killed claiming an exceed of the memory limit (in an extra file generated by slurm, see below). We also tried to allocate more RAM in the NWChem input file without success.

NWChem Imput File:
echo

start Iso7_Ag4Co1

memory stack 500 mb heap 100 mb global 1300 mb


charge 1

#Iso7_Ag4Co1_3_PBE0_def2-tzvpp
geometry units angstrom noautoz noautosym
    Ag  -0.38166698 -1.22599722 2.32396121
    Ag  1.09638904 2.15635599 -1.00068589
    Ag  -2.37929805 -0.99306632 0.63520478
    Ag  1.71495828 -0.16803631 -2.05492258
    Co  0.013174 -0.0583566 -0.02409705
end


#  Def2-TZVPP  EMSL  Basis Set Exchange Library  2/19/18 2:44 AM
# Elements                             References
# --------                             ----------
# H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn: F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys., Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence
# quality for H to Rn: Design and assessment of accuracy 7, 3297 (2005).
#



BASIS "ao basis" PRINT
#BASIS SET: (17s,12p,7d,2f,1g) -> [6s,5p,4d,2f,1g]
Co    S
 325817.0155300              0.22568462484E-03
  48839.6364530              0.17499397533E-02
  11114.9373070              0.91003134097E-02
   3146.1603642              0.36996256837E-01
   1024.4378465              0.12044269621
    368.02508816             0.28598731649
    142.91229205             0.40908312004
     56.482649209            0.21500145739
Co    S
    356.40298318            -0.24767059678E-01
    110.31165215            -0.11702139134
     17.659634834            0.55215522200
      7.5059030479           0.53246877060
Co    S
     11.501807176           -0.22942470077
      1.9081994606           0.71180933514
Co    S
      0.79396696891          1.0000000
Co    S
      0.12444448829          1.0000000
Co    S
      0.44444645379E-01            1.0000000
Co    P
   1731.1369144              0.23905767685E-02
    409.91750438             0.19382999967E-01
    131.45648578             0.90905448509E-01
     48.987439714            0.26146681577
     19.537078992            0.42157264570
      7.9287281634           0.24571813557
Co    P
     31.076017584           -0.29438069973E-01
      4.2835180697           0.55615568168
      1.7022921563           0.96772195064
Co    P
      0.64202908602          1.0000000
Co    P
      0.2421000              1.0000000
Co    P
      0.0913200              1.0000000
Co    D
     68.140745239            0.11983845360E-01
     19.685241019            0.73688540475E-01
      6.9322128825           0.23085496779
      2.6025125694           0.39281059225
Co    D
      0.94016837302          1.0000000
Co    D
      0.30381457794          1.0000000
Co    D
      0.0980000              1.0000000
Co    F
      3.9550000              1.0000000
Co    F
      0.9650000              1.0000000
Co    G
      2.5000000              1.0000000
#BASIS SET: (7s,7p,6d,2f,1g) -> [6s,4p,3d,2f,1g]
Ag    S
     19.000000000           -0.16600104141
     15.428199933            0.35665095918
Ag    S
      6.0553507268           1.0000000
Ag    S
      1.4162368935           1.0000000
Ag    S
      0.61758635858          1.0000000
Ag    S
      0.10474197431          1.0000000
Ag    S
      0.37685106264E-01            1.0000000
Ag    P
     13.188180180            0.66928737147E-01
      7.7952789138          -0.24735235409
      2.0351571912           0.49154280216
      0.98093914842          0.49741609006
Ag    P
      0.44451179958          1.0000000
Ag    P
      0.13000000000          1.0000000
Ag    P
      0.41200000000E-01            1.0000000
Ag    D
     25.784397351            0.35645063082E-02
     11.396636755           -0.12984262784E-01
      2.7345581361           0.24108826548
      1.1873583605           0.42412330744
Ag    D
      0.47316910566          1.0000000
Ag    D
      0.16746017986          1.0000000
Ag    F
      2.5100300              1.0000000
Ag    F
      0.7114200              1.0000000
Ag    G
      1.5619000              1.0000000
END
# Elements                             References
# --------                             ----------
# Y-Cd(ecp-28), Hf-Hg(ecp-46): D. Andrae,U. Haeussermann, M.Dolg, H.Stoll, H.Preuss, Theor.Chim.Acta, 1990, 77, 123?141.
# In-Sb(ecp-28), Tl-Bi(ecp-46): B. Metz, H. Stoll, M. Dolg, J. Chem. Phys., 2000, 113, 2563?2569.
# Te-Xe(ecp-28), Po-Rn(ecp-46): K. A. Peterson, D. Figgen, E. Goll, H. Stoll, M. Dolg, J. Chem. Phys., 2003, 119, 11113?11123.
# Rb(ecp-28), Cs(ecp-46): T.Leininger, A.Nicklass, W.Kuechle, H.Stoll, M.Dolg, A.Bergner, Chem. Phys. Lett., 1996, 255, 274?280.
# Sr(ecp-28), Ba(ecp-46): M. Kaupp, P. V. Schleyer, H. Stoll and H. Preuss, J. Chem. Phys., 1991, 94, 1360?1366.
#



ECP
Ag nelec 28
Ag ul
2     14.2200000            -33.68992012
2      7.1100000             -5.53112021
Ag S
2     13.1300000            255.13936452
2      6.5100000             36.86612154
2     14.2200000             33.68992012
2      7.1100000              5.53112021
Ag P
2     11.7400000            182.18186871
2      6.2000000             30.35775148
2     14.2200000             33.68992012
2      7.1100000              5.53112021
Ag D
2     10.2100000             73.71926087
2      4.3800000             12.50211712
2     14.2200000             33.68992012
2      7.1100000              5.53112021
END


#PBE0
dft
 xc pbe0
 direct
 grid nodisk
 grid xfine
 mult 3
 convergence ncydp 0 dampon 1d99 dampoff 1d-7 damp 70
 iterations 1000
 smear .0010
 print "final evals" "final vectors"
 noio
end

driver
 xyz Iso7_Ag4Co1
 trust 0.3
 tight
end

tddft
 CIS
 nroots 80
end

set lindep:tol 1.0d-7
set int:acc_std double 1d-10
set dft:diisreset 25
unset dft:converged

task tddft energy


Slurm Error Message:
Modules: loading intel/2018u1_mpi
Hint: To start MPI programs, use
- 'mpirun' for tests on the login nodes
- 'srun' in batch jobs
Got  processors.
STARTING
Tue Feb 20 11:56:29 CET 2018
hpb0094
4: WARNING:armci_set_mem_offset: offset changed 367555248128 to 367578845184
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
srun: Job step aborted: Waiting up to 32 seconds for job step to finish.
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
slurmstepd: error: Step 6014759.0 exceeded memory limit (33932900 > 32768000), being killed
slurmstepd: error: *** STEP 6014759.0 ON hpb0094 CANCELLED AT 2018-02-20T12:15:51 ***
slurmstepd: error: Exceeded job memory limit
slurmstepd: error: Exceeded job memory limit
slurmstepd: error: Exceeded job memory limit
slurmstepd: error: Exceeded job memory limit
slurmstepd: error: Exceeded job memory limit
slurmstepd: error: Exceeded job memory limit
srun: error: hpb0094: task 10: Killed
srun: error: hpb0094: tasks 0-6,8-9,11-15: Killed
srun: error: hpb0094: task 7: Killed
FINISHED
Tue Feb 20 12:15:52 CET 2018


Thus, did anyone of you experience a similar problem or has an idea of what may be the cause? Besides that we are interested in restarting TDDFT calculations in general. Are there possibilities for this?

Thank you very much in advance!