Alex Nest
comconadin@gmail.com
We have very strange problem with MCSCF geometry optimization of Fe3S4 cluster (it is kind of protein Fe-S clusters). We have done the following things:
1) first we know (from refs) that our cluster with charge -2 has multiplicity 2.
2) we selected the basis 6-31G** (non-Fe) / LANL2DZ (Fe) and prepare input for C3 symmetry
3) we tried to perform ROHF, but we could not converge it. Only UHF converges but very hard and with very high value of S-SQUARED (~ 6.0 that indicates very large spin contamination). We decided that ground state could be multi-reference and decided to perform MCSCF.
4) we remove one electron and converge RHF for such system
5) then we look at orbitals and selected (3,3) active space
6) then we take vector from (4) step and start MCSCF convergency (it was not hard).
7) then we started MCSCF geometry optimization and faces the following problem:
rms grew:
MAXIMUM GRADIENT = 0.2556168 RMS GRADIENT = 0.0464457
MAXIMUM GRADIENT = 0.2841621 RMS GRADIENT = 0.0537972
MAXIMUM GRADIENT = 0.4198081 RMS GRADIENT = 0.0725880
MAXIMUM GRADIENT = 0.5151014 RMS GRADIENT = 0.0871977
MAXIMUM GRADIENT = 0.5138660 RMS GRADIENT = 0.0859293
MAXIMUM GRADIENT = 0.5365677 RMS GRADIENT = 0.0896454
MAXIMUM GRADIENT = 0.5712724 RMS GRADIENT = 0.0946583
MAXIMUM GRADIENT = 0.6041863 RMS GRADIENT = 0.1003238
MAXIMUM GRADIENT = 0.6494662 RMS GRADIENT = 0.1071054
MAXIMUM GRADIENT = 0.6630896 RMS GRADIENT = 0.1096243
MAXIMUM GRADIENT = 0.6674327 RMS GRADIENT = 0.1108875
MAXIMUM GRADIENT = 0.6796559 RMS GRADIENT = 0.1108236
MAXIMUM GRADIENT = 0.7419342 RMS GRADIENT = 0.1189649
MAXIMUM GRADIENT = 0.7598804 RMS GRADIENT = 0.1230276
MAXIMUM GRADIENT = 0.7938448 RMS GRADIENT = 0.1285953
MAXIMUM GRADIENT = 0.8451196 RMS GRADIENT = 0.1364123
MAXIMUM GRADIENT = 0.8660177 RMS GRADIENT = 0.1402934
MAXIMUM GRADIENT = 0.8763449 RMS GRADIENT = 0.1411417
MAXIMUM GRADIENT = 0.9124437 RMS GRADIENT = 0.1468867
MAXIMUM GRADIENT = 0.9405698 RMS GRADIENT = 0.1504783
MAXIMUM GRADIENT = 0.9340931 RMS GRADIENT = 0.1504645
MAXIMUM GRADIENT = 1.0102995 RMS GRADIENT = 0.1625614
but energy decreased:
NSERCH= 0 ENERGY= -3269.0048828
NSERCH= 1 ENERGY= -3269.0154026
NSERCH= 2 ENERGY= -3269.0019545
NSERCH= 3 ENERGY= -3268.9884073
NSERCH= 4 ENERGY= -3268.9871148
NSERCH= 5 ENERGY= -3268.9903808
NSERCH= 6 ENERGY= -3268.9930019
NSERCH= 7 ENERGY= -3268.9968767
NSERCH= 8 ENERGY= -3268.9989956
NSERCH= 9 ENERGY= -3269.0010380
NSERCH= 10 ENERGY= -3269.0028638
NSERCH= 11 ENERGY= -3269.0016070
NSERCH= 12 ENERGY= -3269.0037472
NSERCH= 13 ENERGY= -3269.0063914
NSERCH= 14 ENERGY= -3269.0094045
NSERCH= 15 ENERGY= -3269.0083837
NSERCH= 16 ENERGY= -3269.0083270
NSERCH= 17 ENERGY= -3269.0083347
NSERCH= 18 ENERGY= -3269.0083693
NSERCH= 19 ENERGY= -3269.0064975
8) we tried SA-MCSCF (adding wstate=1,0.1 to $DET and ntrack=2 to $MCSCF) but approximately the same picture was obtained.
Firefly v.8.1.1 was used. Can you advice something in our case? Could you tell if our modelling strategy is right in global?
Attached please see the input of step (7).
This message contains the 1403 kb attachment [ casopt.inp ] MCSCF optimization from step (7) |