RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

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ndhieu92
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RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by ndhieu92 » 22 Oct 2019, 09:05

WIsh you have a good day everyone.

I am trying to calculate for the spin-orbit coupling constant, but I have got a problem. Eventhough the calculation finished without any error, but the result of SOC value between 2 times of calculation is different between each other. Firstly, I checked the input file (mol. and dal. file) and I am sure that it is correct. So I checked the output file and then I always see the warning is: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS, 60. So now I am trying to add into dal. file: .MAX MICRO ITERATIONS and increase it into 200. Will this fix my problem? I attached 2 output file and also the new dal.file with my thinking. Please let me know your idea.

Thank you so much
Attachments
SPINORBIT_rsplrso_AMFI_quadratic_autosymmetry_MAXMICROITERATIONS.dal
(441 Bytes) Downloaded 9 times
SPINORBIT_rsplrso_AMFI_quadratic_autosymmetry_SOC_BDELA.out
(404.05 KiB) Downloaded 11 times
SPINORBIT_rsplrso_AMFI_quadratic_autosymmetry_2_SOC_BDELA.out
(450.68 KiB) Downloaded 10 times

hjaaj
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by hjaaj » 23 Oct 2019, 13:55

Your spin-orbit coupling constants are garbage, because your calculation is triplet unstable (complex eigenvalues in the calculation of lowest triplet excitation). The differences between the two calculations are caused by numerical noise because of the non-convergence.

Either your DFT iterations do not converge to the ground state (do you get same total energy if you try with another program?), or B3LYP is a bad model for this case.

By the way, your ".MAX IT" keyword has no effect because the ".MAX IT" in that place specify the max. number of geometry iterations in a geometry optimization. But it does not help to increase the correct max iterations for response, because the convergence is stuck because of the above mentioned problems.

ndhieu92
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by ndhieu92 » 23 Oct 2019, 15:05

hjaaj wrote:
23 Oct 2019, 13:55
Your spin-orbit coupling constants are garbage, because your calculation is triplet unstable (complex eigenvalues in the calculation of lowest triplet excitation). The differences between the two calculations are caused by numerical noise because of the non-convergence.

Either your DFT iterations do not converge to the ground state (do you get same total energy if you try with another program?), or B3LYP is a bad model for this case.

By the way, your ".MAX IT" keyword has no effect because the ".MAX IT" in that place specify the max. number of geometry iterations in a geometry optimization. But it does not help to increase the correct max iterations for response, because the convergence is stuck because of the above mentioned problems.
Thank you Dr. Hans for your reply. I am sorry but may I ask you a question: Do you mean the SCF energy which was shown in the output file is total energy? And I am thinking to try with another program like molpro to confirm it. I will try to change to MCSCF to see how it works.

hjaaj
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by hjaaj » 23 Oct 2019, 15:23

I mean this final energy:

Code: Select all

@    Final DFT energy:          -2824.469146640524  
and these final HOMO-LUMO energies:

Code: Select all

    E(LUMO) :    -0.13437205 au (symmetry 1)
  - E(HOMO) :    -0.14494639 au (symmetry 1)
  ------------------------------------------
    gap     :     0.01057434 au
Note that the HOMO and LUMO orbital energies are very close, so no wonder there is triplet instability.

ndhieu92
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by ndhieu92 » 23 Oct 2019, 16:10

hjaaj wrote:
23 Oct 2019, 15:23
I mean this final energy:

Code: Select all

@    Final DFT energy:          -2824.469146640524  
and these final HOMO-LUMO energies:

Code: Select all

    E(LUMO) :    -0.13437205 au (symmetry 1)
  - E(HOMO) :    -0.14494639 au (symmetry 1)
  ------------------------------------------
    gap     :     0.01057434 au
Note that the HOMO and LUMO orbital energies are very close, so no wonder there is triplet instability.
Maybe I will try to recalculate with gaussian 09 software with same basis set B3LYP/6-31G* in dal.file to confirm the DFT energy and HOMO-LUMO energies.
I will keep updating the result.
Thank you so much Dr. Hans

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 02 Nov 2019, 10:55

Dear Prof. Jensen
Could you please give me an rough idea of how large the energy gap between LUMO and HOMO of the triplet state of a molecule would be, because in the uhf spin-flip TDDFT geometry search of that of beta spin orbitals of thiabendazole with PCM, from positive(very small) to negative, also can be very small. [/b]The chief alpha to beta spin-flip may not occur from HOMO to LUMO. The advantage of the spin-flip triplet geometry, MECIs searches lies in it does not need an inital geometry guess.
I will let it supass Cs symmetry beginning and retry.
Last edited by xiongyan21 on 08 Nov 2019, 03:01, edited 3 times in total.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 04 Nov 2019, 02:50

After changing a functional and using C1 symmetry from the very beginning, the successful uhf spin-flip TDDFT search of the triplet state of thiabendazole with PCM using GAMESS gives the beta spin HOMO and LUMO energy -0.273 and -0.135, respectively, and alpha spin HOMO and LUMO energy -0.150 and 0.007, respectively. Of course, spin-flip TDDFT may perfer to some functionals. I use wxMacMolplt to view the orbital energies. The triplet to ground state energy gap got here with 6-31G+(d,p) and true SMD, where there are several warnings in a few steps during optimization, by coincidence, is very close to that got previously with Dunning's basis set, the same functional, and Cs symmetry commence, but false SMD, with each geometry optimized with a differnt method, respectively,
Last edited by xiongyan21 on 10 Nov 2019, 09:06, edited 14 times in total.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 04 Nov 2019, 07:52

I have done the virbational analysis of the triplet state using GAMESS and found there is no imaginary frequence, but it has a warning meaning the Hessian is not very rigorious. Perhaps like the gound state geometry search, a larger basis set can eliminate when a better structure is found. Perhaps with NWCHEM, there is no such warning.
Last edited by xiongyan21 on 09 Nov 2019, 15:05, edited 1 time in total.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 05 Nov 2019, 01:06

It seems this demonstrates what Dr. Schmidt from Ames Lab told me before that HOMO an LUMO are vague concepts, and indeed he is an exert on vitual and occupied orbitals.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 05 Nov 2019, 03:34

Dear Dr. Jensen
Yes, you are right.
I understand it from the article of Prof. Anna Krylov, a very famous theoretist on open-shell and electronically excited species in University of Southern California, the traditional single reference method for excited states will fail when the subspaces of the occupied and virtual become nearly degenerate, which is also true for ground states. Thus, spin-flip methods emerge as times require, and it has been reported to give accurate equilibrium properties and singlet-triplet transition energies of diradicals. According to an published article, SF-TDDFT can only deal with one electron excitation and doubly excited states, but GAMESS can give energie gaps of the singlet to triplet, triplet to triplet, and triplet to mixed.
MCSCF optimization of triplet states may need initial guesses, which are not very easy. I have not tried this using GAMESS.
I think SF-TDDFT can be quite satisfactory since like TDDFT, it can employ the exchange correlation potential to address additional electron correlation effects.
I have already used RHF-TDDFT B3LYP geometry search with GAMESS to find the first singlet excited states of thiabendazole, whose excited energy is close to its fluorescence emission one, although there is also that warning when this geometry is checked for imaginary frequencie.

There is no such warnig at the end of the vibration analysis after the geometry optimization of the ground state of thiabendazole with 6-311G++(2d,2p),
and the excitation energies obtained are not significantly different from tose obtained with the 6-31G optimized geometry, with whcih there is such a warning during vibrational analysis.
Last edited by xiongyan21 on 12 Nov 2019, 13:51, edited 3 times in total.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 08 Nov 2019, 02:29

Can the experimental phosphorescence data be found in literature, so the calculated one can be compared with that?
I can find reference of other molecules, e.g., Porphyrin free base phosphorescence.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 08 Nov 2019, 03:53

Although the test, i.e., UHF SF-TDDFT geometry search of the triplet state of H2CO, has been successful with the two latest GAMESS binaries 2019.R1.P1 for Windows and 2018.R3 for Mac, in the recently released, including 2019.R2 , source code test example, it is noted this example not converged for GCC greater than 4.4.
Thus, perhaps, fix is wanted.
I will try the compilation when I am free.

By the way, the equilibrium geometry of carbendazole obtained by b3lyp with 6-311G++(2d,2p) also has such warning when doing vibrational analysis, and the excitation energy got is very close to that optimized with 6-31G when using the same functional.

In the case of the vibrational small molecule thiol, the 6-311G++(2d, 2p) HF optimized has no such warning, analytically or seminumerically, but the 6-311G++(3df, 2p) optimized does have,To my dismay, the 6-311G++(2d, 2p) optimized using MP2 has, but the 6-311G++(3df, 2p) MP2 optimized has no such a warning when doing it seminumerically using the same large baisi set.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 10 Nov 2019, 10:15

Thiabendazole SF-TDDFT optimized geometry give the triplet to singlet emission energy having a large discrepency of 76 nm from the experimental enhanced data in Determination of thiabendazole in foods and waters by solid-phase transmitted room-temperature phosphorescence.
It is said in the paper the sample and enhancer solutions were deposited on a slip of paper (Whatman No. 4), previously humidified with pH 4.0 acetic/acetate buffer solution, after which the paper was dried and placed between 2 quartz plates. The diffuse transmitted phosphorescence intensity was measured directly at excitation of 303 nm and emission of 472 nm.
Monte Carlo search perhaps is needed for carbendazole first for the ground state due to its rotation, and I will try this.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 12 Nov 2019, 15:28

The article Highly sensitive and selective room-temperature phosphorescence determination of thiabendazole by the supramolecular interaction of thiabendazole/β-cyclodextrin/triton X-100 gives λex/λem = 298/481 nm resulting from a 1 ∶ 1 ∶ 1 β-cyclodextrin (β-CD)/thiabendazole (TBZ)/triton X-100 (TX-100) supramolecular ternary inclusion complex.

Flow injection analysis with on-line nylon powder extraction for room-temperature phosphorescence determination of thiabendazole
gives maximum λem = 505 nm.

hjaaj
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by hjaaj » 12 Nov 2019, 16:15

Dear Yan Xiong

Sorry, but your comments are not really related to the original posting in this thread by Hieu Nguyen. Furthermore, you discuss items (as UHF spin-flip and SF-TDDFT) which are not implemented in dalton, and therefore the dalton forum is not the right place for such a discussion.

xiongyan21
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Re: RSPCTL WARNING-MAXIMUM NUMBER OF MICROITERATIONS

Post by xiongyan21 » 12 Nov 2019, 16:36

Dear Dr. Jensen
Sorry for this.
I will try porphrins' phosphorescence, which has DFT and experimental data, using SF-TDDFT and spin-orbit coupling, respectively, when I am free.

Thanks, anyway.

Very Best Regards!

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