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You can choose an avatar and change the default style by going to "Profile" → "Personality" or "Display".#1 2024-06-27 10:08:46
- u2004376
- Member
- Registered: 2024-04-30
- Posts: 7
convergence issue for state-average optimization
Dear all,
I am new to Molcas and encountered some issues while trying to optimize a singlet biradical, which is not the ground state of the system. Initially, I performed a state-average calculation for the singlet, asking for three roots. The second root corresponded to the singlet biradical with the highest population. I then attempted to optimize the second root using the following input file:
&GATEWAY
Coord=I1a_tripl_hf_orb.xyz
BASIS
cc-pVDZ
Group
nosym
>> Do While
&SEWARD
>> COPY $InDir/$Project.GvOrb INPORB
&RASSCF
LUMORB
Title= I1a_sa_s0_opt
Spin=1; nActEl= 12 0 0; Inactive= 60; Ras2= 12
CiRoot= 3 3 1
Rlxroot= 2
&SLAPAF
>>> EndDo
>> COPY $Project.RasOrb $CurrDir/$Project.s1.RasOrb
>> COPY $Project.JobIph $CurrDir/$Project.s1.JobIph
&GRID_IT
Name
AllThe state-average output resulted in a singlet biradical for root 2 with a weight of 61%.
printout of CI-coefficients larger than 0.05 for root 1
energy= -764.486782
conf/sym 111111111111 Coeff Weight
1 222222000000 0.79326 0.62927
4 22222u00d000 0.10429 0.01088
26 2u2222d00000 -0.07654 0.00586
38 222220200000 -0.10554 0.01114
53 222220u0000d -0.05046 0.00255
83 222u2du0d000 -0.05669 0.00321
143 u2222d200000 0.32535 0.10585
271 222022020000 -0.05659 0.00320
335 u22d22u0d000 0.05685 0.00323
410 u2d222u0000d 0.05255 0.00276
416 202222200000 -0.06021 0.00362
417 202222ud0000 0.05034 0.00253
458 022222200000 -0.14522 0.02109
495 222u2ud0d000 0.05558 0.00309
539 u2222udd0000 -0.13771 0.01896
printout of CI-coefficients larger than 0.05 for root 2
energy= -764.483382
conf/sym 111111111111 Coeff Weight
2 22222ud00000 0.78175 0.61114
32 u22222d00000 0.32882 0.10812
33 u222220d0000 -0.07755 0.00601
41 222220u0d000 -0.16139 0.02605
74 2222udu0000d -0.06370 0.00406
80 222u2d200000 0.05150 0.00265
81 222u2dud0000 0.13937 0.01942
111 22u22du000d0 0.09744 0.00950
123 2u222dud0000 -0.06557 0.00430
128 2u222du00d00 0.07728 0.00597
146 u2222du0d000 0.07597 0.00577
332 u22d22200000 -0.07577 0.00574
461 022222u0d000 0.10322 0.01066
494 222u2udd0000 -0.09893 0.00979
515 22u22ud000d0 -0.05615 0.00315
1405 22202ud20000 -0.07361 0.00542
2040 02222ud02000 -0.07229 0.00523
printout of CI-coefficients larger than 0.05 for root 3
energy= -764.413446
conf/sym 111111111111 Coeff Weight
1 222222000000 0.10284 0.01058
4 22222u00d000 -0.18033 0.03252
6 22222u0000d0 0.07567 0.00573
14 222u22d00000 0.43281 0.18733
15 222u220d0000 -0.08404 0.00706
38 222220200000 0.66334 0.44002
39 222220ud0000 0.13543 0.01834
40 222220020000 -0.11071 0.01226
62 2222udu0d000 0.05407 0.00292
101 22u22d200000 0.06418 0.00412
143 u2222d200000 -0.15458 0.02389
144 u2222dud0000 0.05054 0.00255
158 u2222du0000d -0.07161 0.00513
269 222022200000 -0.15653 0.02450
312 2u2d22ud0000 -0.08098 0.00656
335 u22d22u0d000 0.05304 0.00281
500 222u2ud000d0 0.05016 0.00252
539 u2222udd0000 -0.09754 0.00951
549 u2222ud0000d 0.06012 0.00361To obtain a more accurate geometry of this biradical state, I tried giving full weight to the root 2 and attempted optimization with the following input file:
&GATEWAY
Coord=I1a_tripl_hf_orb.xyz
BASIS
cc-pVDZ
Group
nosym
>> Do While
&SEWARD
>> COPY $InDir/$Project.GvOrb INPORB
&RASSCF
LUMORB
Title= I1a_sa_s0_opt
Spin=1; nActEl= 12 0 0; Inactive= 60; Ras2= 12
CiRoot
2 2
1 2
0 1
Rlxroot= 2
&SLAPAF
>>> EndDo
>> COPY $Project.RasOrb $CurrDir/$Project.s1.RasOrb
>> COPY $Project.JobIph $CurrDir/$Project.s1.JobIph
&GRID_IT
Name
AllHowever, I am facing convergence issues:
&SLAPAF
only a single process is used, running in SERIAL mode
available to each process: 19 GB of memory, 1 thread?
pid: 9061
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
**********************************************************************************************************************
* Energy Statistics for Geometry Optimization *
**********************************************************************************************************************
Energy Grad Grad Step Estimated Geom Hessian
Iter Energy Change Norm Max Element Max Element Final Energy Update Update Index
1 -764.46592024 0.00000000 0.175371 -0.051614 nrc004 -0.080325 nrc004 -764.47603982 RS-RFO None 0
2 -764.48021624 -0.01429600 0.089457 0.033314 nrc004 0.100246 nrc004 -764.48448251 RS-RFO BFGS 0
3 -764.47601376 0.00420248 0.139537 0.047560 nrc002 -0.054965 nrc011 -764.47731232 RS-RFO BFGS 0
4 -764.48280130 -0.00678754 0.074818 -0.021849 nrc003 -0.022324 nrc011 -764.48349286 RS-RFO BFGS 0
5 -764.48168139 0.00111991 0.079680 0.021988 nrc004 0.137724 nrc004 -764.48561104 RS-RFO BFGS 0
6 -764.43850721 0.04317418 0.186921 -0.077062 nrc005 -0.113792 nrc003 -764.48261422 RS-RFO BFGS 0
7 -764.48303304 -0.04452583 0.063573 0.018867 nrc004 0.202224* nrc049 -764.48601809 RS-RFO BFGS 0
8 -764.48249270 0.00054034 0.041241 -0.012619 nrc067 -0.225743* nrc049 -764.48406587 RS-RFO BFGS 0
9 -764.48208786 0.00040483 0.056746 -0.021361 nrc066 0.210770 nrc049 -764.48352446 RS-RFO BFGS 0
10 -764.48279516 -0.00070729 0.155498 0.053428 nrc003 0.026739* nrc066 -764.48372818 RS-RFO BFGS 0
11 -764.48354865 -0.00075349 0.037125 0.008534 nrc011 -0.099886* nrc049 -764.48418231 RS-RFO BFGS 0
12 -764.46782263 0.01572602 0.148026 0.052948 nrc005 0.210740* nrc049 -764.48431708 RS-RFO BFGS 0
13 -764.48346531 -0.01564269 0.040172 -0.010248 nrc003 0.090583* nrc066 -764.48371983 RS-RFO BFGS 0
14 -764.48319616 0.00026916 0.103712 -0.035177 nrc003 -0.201036* nrc049 -764.48431212 RS-RFO BFGS 0
15 -764.47849067 0.00470549 0.129536 -0.039215 nrc003 0.150025* nrc066 -764.48419851 RS-RFO BFGS 0
16 -764.47672534 0.00176533 0.114616 -0.033642 nrc003 -0.239660* nrc049 -764.47970318 RS-RFO BFGS 0
17 -764.47741489 -0.00068955 0.070171 0.018647 nrc005 0.106999* nrc066 -764.47835653 RS-RFO BFGS 0
18 -764.48328200 -0.00586712 0.120531 -0.039231 nrc003 0.049205* nrc060 -764.48464590 RS-RFO BFGS 0
19 -764.47970812 0.00357389 0.073471 0.023961 nrc005 -0.161111* nrc060 -764.48560148 RS-RFO BFGS 0
20 -764.48178445 -0.00207633 0.040735 -0.009225 nrc074 -0.123157* nrc066 -764.48306827 RS-RFO BFGS 0
21 -764.48036605 0.00141839 0.031744 0.008371 nrc067 0.316040* nrc066 -764.48397269 RS-RFO BFGS 0
22 -764.48197806 -0.00161201 0.160121 -0.057457 nrc003 0.080950* nrc060 -764.48371043 RS-RFO BFGS 0
23 -764.48338653 -0.00140847 0.057718 -0.013331 nrc001 0.047843 nrc011 -764.48493229 RS-RFO BFGS 0
24 -764.48189855 0.00148798 0.136189 -0.041372 nrc002 0.125833* nrc047 -764.48467971 RS-RFO BFGS 0
25 -764.48117259 0.00072596 0.161816 -0.054694 nrc001 -0.091849* nrc049 -764.48269155 RS-RFO BFGS 0
26 -764.48003624 0.00113635 0.127236 0.041001 nrc001 0.198734* nrc049 -764.48755723 RS-RFO BFGS 0
27 -764.47981327 0.00022298 0.074102 -0.015326 nrc066 -0.207269 nrc049 -764.48106519 RS-RFO BFGS 0
28 -764.48213197 -0.00231870 0.054081 -0.022226 nrc074 0.053218* nrc073 -764.48447369 RS-RFO BFGS 0
29 -764.48397352 -0.00184155 0.033153 0.010347 nrc001 -0.116894* nrc049 -764.48441209 RS-RFO BFGS 0
30 -764.47849135 0.00548216 0.163248 0.042423 nrc001 -0.072786* nrc049 -764.48614294 RS-RFO BFGS 0(1)
31 -764.47580926 0.00268210 0.142234 -0.045431 nrc004 -0.084255 nrc055 -764.47655809 RS-RFO BFGS 0
32 -764.48224070 -0.00643145 0.086963 -0.028147 nrc003 0.160285 nrc049 -764.48572672 RS-RFO BFGS 0
33 -764.48391340 -0.00167270 0.096246 -0.036249 nrc001 0.098546* nrc049 -764.48532856 RS-RFO BFGS 0(1)
34 -764.45432335 0.02959005 0.139948 0.038362 nrc005 -0.119109 nrc067 -764.46422798 RS-RFO BFGS 0(1)
35 -764.47327938 -0.01895603 0.129427 -0.040020 nrc004 -0.080101* nrc049 -764.47754906 RS-RFO BFGS 0(1)
36 -764.47734577 -0.00406640 0.085489 -0.021356 nrc067 0.155796* nrc049 -764.48216256 RS-RFO BFGS 0(1)
37 -764.47975860 -0.00241283 0.097621 0.020783 nrc025 0.090761 nrc046 -764.48313455 RS-RFO BFGS 0(1)
38 -764.48259371 -0.00283511 0.047310 -0.011574 nrc001 0.065947 nrc049 -764.48353539 RS-RFO BFGS 0
39 -764.47979374 0.00279997 0.113832 0.034461 nrc003 -0.207524 nrc049 -764.48607211 RS-RFO BFGS 0
+----------------------------------+----------------------------------+
+ Cartesian Displacements + Gradient in internals +
+ Value Threshold Converged? + Value Threshold Converged? +
+-----+----------------------------------+----------------------------------+
+ RMS + 9.3163E-02 1.2000E-03 No + 1.1999E-02 3.0000E-04 No +
+-----+----------------------------------+----------------------------------+
+ Max + 1.5863E-01 1.8000E-03 No + 3.4461E-02 4.5000E-04 No +
+-----+----------------------------------+----------------------------------+
Convergence not reached yet!Any suggestions to solve this issue (scientific/technical) would be highly appreciated!
Thanks!
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#2 2024-06-27 10:48:13
- Ignacio
- Administrator
- From: Uppsala
- Registered: 2015-11-03
- Posts: 1,083
Re: convergence issue for state-average optimization
Using a single-root approach for an excited state is risky. There will often be convergence issues in the RASSCF calculation already, if not root flips. Even with a state-averaged approach, you may also encounter root flipping during the geometry optimization. For this latter problem, you may try the TRACK keyword in SLAPAF. Possibly you'll need to examine your system/orbitals at every iteration and make sure the correct state is chosen at every step.
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#3 2024-06-27 11:14:33
- u2004376
- Member
- Registered: 2024-04-30
- Posts: 7
Re: convergence issue for state-average optimization
Thank you very much for the suggestion! I will try tracking the electronic states during the optimization to see if this is the issue.
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