(Solved) Energy increases with task dft optimize


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Just Got Here
Hi,

I tried geometry optimization with a small molecule, and I found that energy increases with task dft optimize. I tried task scf optimize and energy decreased in that case. Am I missing something here? I really appreciate any help you can provide. Here's the input script for task dft optimize. Version is 6.6 and I applied patch released on 28th Jan.

title "NPB (neutral) optimization"
memory 2048 mb

start npb_oo

charge 0

geometry units angstroms autoz nocenter noautosym
    C18      0.535700023    2.266299963    0.547900021
    C17     -0.529100001    1.594200015    1.152699947
    C22     -0.342700005    0.264999986    1.541499972
    C21      0.870500028   -0.366499990    1.332299948
    C20      1.950399995    0.298900008    0.739700019
    C19      1.750100017    1.629500031    0.355199993
    H13      0.404399991    3.288100004    0.219799995
    H16     -1.156000018   -0.266400009    2.017100096
    H15      0.994700015   -1.386899948    1.671300054
    H14      2.548000097    2.165699959   -0.142399997
    C42      3.244199991   -0.375099987    0.529999971
    C43      4.454500198    0.321000010    0.636200011
    H31      4.444200039    1.368899941    0.906199992
    C44      5.671800137   -0.311100006    0.452899992
    H32      6.593299866    0.245499998    0.557699978
    C39      5.727000237   -1.672299981    0.141200006
    C41      3.313899994   -1.737599969    0.217999995
    H30      2.399100065   -2.301199913    0.088299997
    C40      4.526599884   -2.376399994    0.018800000
    H29      4.546999931   -3.424799919   -0.243599996
    N2       6.976500034   -2.296499968   -0.060800001
    N1      -1.778699994    2.217200041    1.356999993
    C31      7.958300114   -1.608399987   -0.826300025
    C30      7.642799854   -1.141299963   -2.080699921
    H23      6.645899773   -1.308799982   -2.466399908
    C32      9.259599686   -1.389199972   -0.285899997
    C27     10.227499962   -0.716899991   -1.093099952
    C28      9.864000320   -0.259099990   -2.381799936
    H21     10.604399681    0.256199986   -2.981199980
    C29      8.594499588   -0.456299990   -2.857899904
    H22      8.318499565   -0.101499997   -3.842499971
    C33      7.190299988   -3.645100117    0.287600011
    C38      6.621699810   -4.180300236    1.449499965
    H28      5.999000072   -3.554899931    2.073999882
    C34      8.008899689   -4.459700108   -0.499000013
    H24      8.457799911   -4.055300236   -1.395300031
    C37      6.857200146   -5.500400066    1.800400019
    H27      6.409299850   -5.895699978    2.703399897
    C36      7.674499989   -6.309299946    1.016000032
    H26      7.860599995   -7.337299824    1.297099948
    C35      8.250800133   -5.776199818   -0.130300000
    H25      8.889499664   -6.390399933   -0.752600014
    C11     -1.879600048    3.589200020    1.659999967
    C12     -2.951600075    4.344799995    1.177600026
    H8      -3.690999985    3.875400066    0.543900013
    C13     -3.073299885    5.685800076    1.515400052
    H9      -3.913100004    6.252600193    1.133399963
    C14     -2.127399921    6.302499771    2.324899912
    H10     -2.223200083    7.348800182    2.582600117
    C15     -1.056599975    5.553199768    2.803400040
    H11     -0.315499991    6.014299870    3.444200039
    C16     -0.934000015    4.209700108    2.484899998
    H12     -0.108499996    3.632100105    2.876600027
    C9      -2.957000017    1.478899956    1.057899952
    C8      -3.112799883    0.917299986   -0.187500000
    H7      -2.330100060    1.049499989   -0.922599971
    C7      -4.268499851    0.182799995   -0.509899974
    H6      -4.365600109   -0.246000007   -1.498999953
    C6      -5.270500183    0.029700000    0.411900014
    H5      -6.168099880   -0.523500025    0.164499998
    C10     -3.964099884    1.308200002    2.052799940
    C5      -5.145800114    0.583599985    1.707999945
    C1      -3.832099915    1.806900024    3.370699883
    H1      -2.934499979    2.341099977    3.644000053
    C2      -4.826399803    1.618800044    4.295199871
    H2      -4.707300186    2.004499912    5.299499989
    C3      -6.004499912    0.925000012    3.949399948
    H3      -6.784699917    0.789499998    4.687399864
    C4      -6.155799866    0.417299986    2.686300039
    H4      -7.052800179   -0.126900002    2.416399956
    C23      9.624500275   -1.790300012    1.021499991
    H17      8.893199921   -2.282999992    1.644400001
    C24     10.888400078   -1.559800029    1.499199986
    H18     11.149600029   -1.871000051    2.502500057
    C25     11.852800369   -0.918299973    0.694500029
    H19     12.848999977   -0.748199999    1.082200050
    C26     11.525699615   -0.504000008   -0.569299996
    H20     12.256999969    0.000600000   -1.188899994
end

basis "ao basis" cartesian
    C library 3-21g
    H library 3-21g
    N library 3-21g
end

set lindep:tol 1e-4

dft
   mult 1
   grid fine
   iterations 50
   convergence energy 1e-6
   xc pbe0
   cs00
end

driver
    loose
    maxiter 500
end

task dft optimize


And here's the input script for task scf optimize.


title "NPB (neutral) optimization"
memory 2048 mb

start npb_oo

charge 0

geometry units angstroms autoz nocenter noautosym
    C18      0.535700023    2.266299963    0.547900021
    C17     -0.529100001    1.594200015    1.152699947
    C22     -0.342700005    0.264999986    1.541499972
    C21      0.870500028   -0.366499990    1.332299948
    C20      1.950399995    0.298900008    0.739700019
    C19      1.750100017    1.629500031    0.355199993
    H13      0.404399991    3.288100004    0.219799995
    H16     -1.156000018   -0.266400009    2.017100096
    H15      0.994700015   -1.386899948    1.671300054
    H14      2.548000097    2.165699959   -0.142399997
    C42      3.244199991   -0.375099987    0.529999971
    C43      4.454500198    0.321000010    0.636200011
    H31      4.444200039    1.368899941    0.906199992
    C44      5.671800137   -0.311100006    0.452899992
    H32      6.593299866    0.245499998    0.557699978
    C39      5.727000237   -1.672299981    0.141200006
    C41      3.313899994   -1.737599969    0.217999995
    H30      2.399100065   -2.301199913    0.088299997
    C40      4.526599884   -2.376399994    0.018800000
    H29      4.546999931   -3.424799919   -0.243599996
    N2       6.976500034   -2.296499968   -0.060800001
    N1      -1.778699994    2.217200041    1.356999993
    C31      7.958300114   -1.608399987   -0.826300025
    C30      7.642799854   -1.141299963   -2.080699921
    H23      6.645899773   -1.308799982   -2.466399908
    C32      9.259599686   -1.389199972   -0.285899997
    C27     10.227499962   -0.716899991   -1.093099952
    C28      9.864000320   -0.259099990   -2.381799936
    H21     10.604399681    0.256199986   -2.981199980
    C29      8.594499588   -0.456299990   -2.857899904
    H22      8.318499565   -0.101499997   -3.842499971
    C33      7.190299988   -3.645100117    0.287600011
    C38      6.621699810   -4.180300236    1.449499965
    H28      5.999000072   -3.554899931    2.073999882
    C34      8.008899689   -4.459700108   -0.499000013
    H24      8.457799911   -4.055300236   -1.395300031
    C37      6.857200146   -5.500400066    1.800400019
    H27      6.409299850   -5.895699978    2.703399897
    C36      7.674499989   -6.309299946    1.016000032
    H26      7.860599995   -7.337299824    1.297099948
    C35      8.250800133   -5.776199818   -0.130300000
    H25      8.889499664   -6.390399933   -0.752600014
    C11     -1.879600048    3.589200020    1.659999967
    C12     -2.951600075    4.344799995    1.177600026
    H8      -3.690999985    3.875400066    0.543900013
    C13     -3.073299885    5.685800076    1.515400052
    H9      -3.913100004    6.252600193    1.133399963
    C14     -2.127399921    6.302499771    2.324899912
    H10     -2.223200083    7.348800182    2.582600117
    C15     -1.056599975    5.553199768    2.803400040
    H11     -0.315499991    6.014299870    3.444200039
    C16     -0.934000015    4.209700108    2.484899998
    H12     -0.108499996    3.632100105    2.876600027
    C9      -2.957000017    1.478899956    1.057899952
    C8      -3.112799883    0.917299986   -0.187500000
    H7      -2.330100060    1.049499989   -0.922599971
    C7      -4.268499851    0.182799995   -0.509899974
    H6      -4.365600109   -0.246000007   -1.498999953
    C6      -5.270500183    0.029700000    0.411900014
    H5      -6.168099880   -0.523500025    0.164499998
    C10     -3.964099884    1.308200002    2.052799940
    C5      -5.145800114    0.583599985    1.707999945
    C1      -3.832099915    1.806900024    3.370699883
    H1      -2.934499979    2.341099977    3.644000053
    C2      -4.826399803    1.618800044    4.295199871
    H2      -4.707300186    2.004499912    5.299499989
    C3      -6.004499912    0.925000012    3.949399948
    H3      -6.784699917    0.789499998    4.687399864
    C4      -6.155799866    0.417299986    2.686300039
    H4      -7.052800179   -0.126900002    2.416399956
    C23      9.624500275   -1.790300012    1.021499991
    H17      8.893199921   -2.282999992    1.644400001
    C24     10.888400078   -1.559800029    1.499199986
    H18     11.149600029   -1.871000051    2.502500057
    C25     11.852800369   -0.918299973    0.694500029
    H19     12.848999977   -0.748199999    1.082200050
    C26     11.525699615   -0.504000008   -0.569299996
    H20     12.256999969    0.000600000   -1.188899994
end

basis "ao basis" cartesian
    C library 3-21g
    H library 3-21g
    N library 3-21g
end

set lindep:tol 1e-4

scf
    singlet
    rhf
    sym on
    adapt on
end

driver
    loose
    maxiter 500
end

task scf optimize


With task dft optimize, energy increases monotonically like this (first 10 steps)

@ Step       Energy      Delta E   Gmax     Grms     Xrms     Xmax   Walltime
@ ---- ---------------- -------- -------- -------- -------- -------- --------
@    0   -1793.46478631  0.0D+00  0.10430  0.03824  0.00000  0.00000    105.8
@    1   -1793.38156185  8.3D-02  0.07246  0.02674  0.21331  0.57562    299.9
@    2   -1793.35223820  2.9D-02  0.06529  0.02469  0.05668  0.18570    481.9
@    3   -1793.33901366  1.3D-02  0.06270  0.02382  0.02046  0.06515    618.9
@    4   -1793.33177032  7.2D-03  0.06145  0.02336  0.01051  0.03215    755.6
@    5   -1793.32473913  7.0D-03  0.06059  0.02292  0.00836  0.02475    872.2
@    6   -1793.31745770  7.3D-03  0.05967  0.02248  0.00891  0.02518   1008.5
@    7   -1793.31000709  7.5D-03  0.05899  0.02202  0.00814  0.02170   1117.1
@    8   -1793.30248781  7.5D-03  0.05833  0.02158  0.00874  0.02312   1262.3
@    9   -1793.29509830  7.4D-03  0.05783  0.02115  0.00807  0.02058   1372.2
@   10   -1793.28780440  7.3D-03  0.05734  0.02074  0.00802  0.02156   1496.3


And this is the first 10 steps of task scf optimize

@ Step       Energy      Delta E   Gmax     Grms     Xrms     Xmax   Walltime
@ ---- ---------------- -------- -------- -------- -------- -------- --------
@    0   -1783.77043760  0.0D+00  0.01359  0.00351  0.00000  0.00000     54.9
@    1   -1783.77748243 -7.0D-03  0.00189  0.00039  0.07169  0.23144    105.1
@    2   -1783.77805208 -5.7D-04  0.00270  0.00047  0.07835  0.30788    168.6
@    3   -1783.77850695 -4.5D-04  0.00151  0.00030  0.07608  0.21305    231.8
@    4   -1783.77867721 -1.7D-04  0.00133  0.00020  0.03582  0.11061    308.0
@    5   -1783.77873114 -5.4D-05  0.00036  0.00008  0.02033  0.06098    380.9
@    6   -1783.77878076 -5.0D-05  0.00091  0.00014  0.03627  0.12434    445.9
@    7   -1783.77882004 -3.9D-05  0.00074  0.00012  0.04230  0.14288    483.2
@    8   -1783.77884784 -2.8D-05  0.00046  0.00005  0.03545  0.12971    522.7
@    9   -1783.77885345 -5.6D-06  0.00018  0.00002  0.01095  0.04002    587.9
@   10   -1783.77886111 -7.7D-06  0.00022  0.00004  0.00713  0.02373    627.6