[Pw_forum] bfgs optimization not going anywhere

Giuseppe Mattioli giuseppe.mattioli at ism.cnr.it
Tue Nov 24 10:53:05 CET 2015


Dear Matej
I do not see anything particularly wrong in your input. But you are putting together a lot of things that do not make convergence easier...
1) open shell (are you sure you need it even if your total number of electrons is odd?)
2) dipole correction (maybe you can add the correction after a bit of optimization...)
3) k-points (block all the metal atoms and use gamma only. Then refine the optimization, if you are sure you need dispersion, or perform a nscf 
calculation to have DOS or whatever)
4) DFT-D2 (known huge overestimation of metal-molecule interaction, see Grimme's 2010 paper if I remember well. vdwdf is better for such systems, and 
the open-shell implementation has been recently added to the code).
You may try to switch off one or two of such features and see what happens. It is not a solution to your problem, I know...
HTH
Giuseppe
 

On Tuesday, November 24, 2015 09:43:02 AM Matej Huš wrote:
> Dear PW community
> 
> I have a problem when trying to find optimized geometry of an adsorbed
> intermediate in "benzene" hydrogenation on Ru surface (see input below).
> 
> I believe I am fairly close to optimised structure since I'm only adding one
> hydrogen  atom to an already optimised reactant and only slight displacing
> the adjacent atoms.
> 
> 
> 
> The problem is that BFGS doesn't seem to go anywhere. Energy only
> fluctuates, which to my understanding is a sign of being close to a minimum.
> However, forces remain large.
> 
> 
> 
> I've switched to the damp algorithm and the problem persists. I've searched
> through the forum and the usual approaches of tackling this issue do not
> seem to work.
> 
> 
> 
> Any ideas? Thank you!
> 
> Matej Hus
> 
> Laboratory of Catalysis and Chemcial Reaction Engineering
> 
> National Institute of Chemistry
> 
> Ljubljana, Slovenia
> 
> 
> 
> OUTPUT:
> 
> Total force =     0.377547     Total SCF correction =     0.000233
> 
> Total force =     0.290735     Total SCF correction =     0.000272
> 
> Total force =     0.292438     Total SCF correction =     0.000238
> 
> Total force =     0.338997     Total SCF correction =     0.000229
> 
> Total force =     0.358435     Total SCF correction =     0.000297
> 
> Total force =     0.337403     Total SCF correction =     0.000028
> 
> Total force =     0.348615     Total SCF correction =     0.000012
> 
> Total force =     0.353731     Total SCF correction =     0.000027
> 
> Total force =     0.356168     Total SCF correction =     0.000037
> 
> Total force =     0.357346     Total SCF correction =     0.000022
> 
> Total force =     0.357909     Total SCF correction =     0.000028
> 
> Total force =     0.358211     Total SCF correction =     0.000040
> 
> Total force =     0.358327     Total SCF correction =     0.000048
> 
> Total force =     0.358419     Total SCF correction =     0.000029
> 
> Total force =     0.288584     Total SCF correction =     0.000013
> 
> Total force =     0.281519     Total SCF correction =     0.000024
> 
>   Total force =     0.325271     Total SCF correction =     0.000022
> 
>   Total force =     0.342948     Total SCF correction =     0.000049
> 
>   Total force =     0.350916     Total SCF correction =     0.000026
> 
>   Total force =     0.354742     Total SCF correction =     0.000015
> 
> 
> 
> total energy              =   -7426.57738045 Ry
> 
> total energy              =   -7426.51356677 Ry
> 
> total energy              =   -7426.57388244 Ry
> 
> total energy              =   -7426.57758011 Ry
> 
> total energy              =   -7426.57784907 Ry
> 
> total energy              =   -7426.57707917 Ry
> 
> total energy              =   -7426.57763184 Ry
> 
> total energy              =   -7426.57777696 Ry
> 
> total energy              =   -7426.57782155 Ry
> 
> total energy              =   -7426.57783739 Ry
> 
> total energy              =   -7426.57784377 Ry
> 
> total energy              =   -7426.57784657 Ry
> 
> total energy              =   -7426.57784787 Ry
> 
> total energy              =   -7426.57784849 Ry
> 
> total energy              =   -7426.51197755 Ry
> 
> total energy              =   -7426.57231380 Ry
> 
>   total energy              =   -7426.57690438 Ry
> 
>   total energy              =   -7426.57767359 Ry
> 
>   total energy              =   -7426.57782320 Ry
> 
>   total energy              =   -7426.57785046 Ry
> 
> 
> 
> 
> 
> 
> 
> INPUT
> 
> 
> 
> &CONTROL
> 
>                  calculation = 'relax' ,
> 
>                 restart_mode = 'from_scratch' ,
> 
>                       outdir = './tmp/$filename/' ,
> 
>                   pseudo_dir = '../../pseudo/' ,
> 
>                       prefix = '$PROJECT.$PREFIX' ,
> 
>                      tstress = .true. ,
> 
>                      tprnfor = .true. ,
> 
>                                                            tefield = .true.
> ,
> 
>                                                            dipfield = .true.
> ,
> 
>                                          wf_collect = .true. ,
> 
>                                       forc_conv_thr = 1.0d-2 ,
> 
>                                       etot_conv_thr = 1.0d-3 ,
> 
> /
> 
> &SYSTEM
> 
>                        ibrav = 0,
> 
>                          nat = 169,
> 
>                         ntyp = 4,
> 
>                      ecutwfc = 50. ,
> 
>                      ecutrho = 400. ,
> 
>                  occupations = 'smearing' ,
> 
>                      degauss = 0.01 ,
> 
>                     smearing = 'gaussian' ,
> 
>                            nspin = 2,
> 
>                            starting_magnetization(3) = 0.1D0,
> 
> 
>                             edir = 3 ,
> 
>                          emaxpos = 0.70 ,
> 
>                           eopreg = 0.10 ,
> 
>                             eamp = 0. ,
> 
>                         vdw_corr = 'grimme-d2' ,
> 
> /
> 
> &ELECTRONS
> 
>                     conv_thr = 1.0d-8 ,
> 
>                  mixing_mode = 'local-TF' ,
> 
>                  mixing_beta = 0.7 ,
> 
>              diagonalization = 'david' ,
> 
> /
> 
> &IONS
> 
>                            ion_dynamics = 'bfgs'
> 
> /
> 
> ATOMIC_SPECIES
> 
>   C  12.0107   C.pbe-van_ak.UPF
> 
>   O  15.9994   O.pbe-van_ak.UPF
> 
>   H  1.00794   H.pbe-van_ak.UPF
> 
>   Ru 101.07  Ru.pbe-n-van.UPF
> 
> CELL_PARAMETERS (angstrom)
> 
>   16.321200000000001        0.0000000000000000        0.0000000000000000
> 
> 
>   -8.1603024666000010        14.134052780999999        0.0000000000000000
> 
> 
>    0.0000000000000000        0.0000000000000000        16.449990000000000
> 
> 
> ATOMIC_POSITIONS {angstrom}
> 
> C   3.823435   4.428351  -2.238119
> 
> C   4.207660   7.066097  -1.957571
> 
> C   5.382535   6.245297  -2.046714
> 
> C   2.826156   6.592102  -2.044417
> 
> C   2.605150   5.211015  -1.862465
> 
> C   5.239533   4.845664  -1.857622
> 
> H   6.289090   6.563743  -2.479089
> 
> H   2.056333   7.198156  -2.447744
> 
> H   5.901797   4.091352  -2.346132
> 
> C   4.356069   8.532511  -2.316072
> 
> H   4.612650   8.548608  -3.368310
> 
> H   3.373673   9.046938  -2.254871
> 
> C   5.463282   9.426981  -1.698096
> 
> H   6.495975   8.975869  -1.885484
> 
> C   5.405119  10.834051  -2.080030
> 
> H   6.295699  11.303877  -2.501651
> 
> H   4.458970  11.177894  -2.511771
> 
> O   1.435424   4.469087  -2.181152
> 
> O   3.856994   4.338965  -3.691012
> 
> H   3.056321   3.845227  -3.936256
> 
> C   0.279435   5.298750  -2.364509
> 
> H   0.319958   6.268073  -1.757642
> 
> H  -0.601019   4.681992  -2.169727
> 
> H   0.256687   5.698418  -3.369246
> 
> Ru      -0.001369337   1.556584593   0.075560866
> 
> Ru      -0.000332396   1.570948941   4.343508964
> 
> Ru       1.365399095   0.783715910   2.186895546
> 
> Ru       1.360130130   0.785217302   6.450041079    0   0   0
> 
> Ru      -1.395141299   3.901664942   0.104266016
> 
> Ru      -1.358003051   3.925332407   4.347877622
> 
> Ru       0.001086078   3.133790672   2.185915046
> 
> Ru       0.000079719   3.140892766   6.450041079    0   0   0
> 
> Ru      -2.734179783   6.282896555   0.078376985
> 
> Ru      -2.720474098   6.281410601   4.344732131
> 
> Ru      -1.371333197   5.496660844   2.194198333
> 
> Ru      -1.359970692   5.496568229   6.450041079    0   0   0
> 
> Ru      -4.075816415   8.634392357   0.072172378
> 
> Ru      -4.079453331   8.635363049   4.344025158
> 
> Ru      -2.722886017   7.851015877   2.186163273
> 
> Ru      -2.720021103   7.852243693   6.450041079    0   0   0
> 
> Ru      -5.438087227  10.991883567   0.073453130
> 
> Ru      -5.440646605  10.991998561   4.342465402
> 
> Ru      -4.077621786  10.206705204   2.182915408
> 
> Ru      -4.080071514  10.207919156   6.450041079    0   0   0
> 
> Ru      -6.797369367  13.348181237   0.072990617
> 
> Ru      -6.801031281  13.350484654   4.345639267
> 
> Ru      -5.436787433  12.561653380   2.179262317
> 
> Ru      -5.440121925  12.563594620   6.450041079    0   0   0
> 
> Ru       2.715311852   1.527647616   0.101989659
> 
> Ru       2.720550343   1.570752007   4.343568642
> 
> Ru       4.083701186   0.788237572   2.191274875
> 
> Ru       4.080330130   0.785217302   6.450041079    0   0   0
> 
> Ru       1.332796727   3.884730461   0.108449956
> 
> Ru       1.359815757   3.925053389   4.348864911
> 
> Ru       2.724454938   3.135003661   2.187748195
> 
> Ru       2.720279719   3.140892766   6.450041079    0   0   0
> 
> Ru      -0.036540681   6.293690017   0.113273071
> 
> Ru       0.000250876   6.283398964   4.341473656
> 
> Ru       1.368363479   5.492984760   2.210886929
> 
> Ru       1.360229308   5.496568229   6.450041079    0   0   0
> 
> Ru      -1.360181166   8.645849465   0.076512823
> 
> Ru      -1.358220502   8.635315522   4.345131190
> 
> Ru       0.003606413   7.857454617   2.180903123
> 
> Ru       0.000178897   7.852243693   6.450041079    0   0   0
> 
> Ru      -2.717550655  10.991441853   0.074578409
> 
> Ru      -2.719667640  10.994672359   4.343879458
> 
> Ru      -1.363703428  10.205564339   2.180413112
> 
> Ru      -1.359871514  10.207919156   6.450041079    0   0   0
> 
> Ru      -4.079425193  13.348859379   0.073102562
> 
> Ru      -4.078243428  13.348918804   4.343696706
> 
> Ru      -2.716957713  12.559541929   2.180220058
> 
> Ru      -2.719921925  12.563594620   6.450041079    0   0   0
> 
> Ru       5.444305011   1.544140673   0.077580391
> 
> Ru       5.441262148   1.570210548   4.345124348
> 
> Ru       6.799253570   0.780757966   2.174142918
> 
> Ru       6.800530130   0.785217302   6.450041079    0   0   0
> 
> Ru       4.101075051   3.918487481   0.089328061
> 
> Ru       4.080503512   3.922448428   4.345807657
> 
> Ru       5.453996130   3.132523123   2.203765433
> 
> Ru       5.440479719   3.140892766   6.450041079    0   0   0
> 
> Ru       2.693781051   6.301502557   0.080052232
> 
> Ru       2.719965269   6.285376244   4.346166655
> 
> Ru       4.082545252   5.495838294   2.230179298
> 
> Ru       4.080429308   5.496568229   6.450041079    0   0   0
> 
> Ru       1.333524093   8.673068207   0.090057277
> 
> Ru       1.361314630   8.639443068   4.351871754
> 
> Ru       2.713937768   7.851947852   2.205515356
> 
> Ru       2.720378897   7.852243693   6.450041079    0   0   0
> 
> Ru       0.002938643  10.992338155   0.068816656
> 
> Ru       0.002246837  10.992781035   4.345012471
> 
> Ru       1.359046268  10.202045681   2.173065312
> 
> Ru       1.360328486  10.207919156   6.450041079    0   0   0
> 
> Ru      -1.354515229  13.346965578   0.075509661
> 
> Ru      -1.358807460  13.349373114   4.343294393
> 
> Ru       0.000846349  12.564362626   2.182306066
> 
> Ru       0.000278075  12.563594620   6.450041079    0   0   0
> 
> Ru       8.162177605   1.566177227   0.071766246
> 
> Ru       8.159873412   1.569936529   4.345021195
> 
> Ru       9.520566278   0.786144384   2.181250719
> 
> Ru       9.520730130   0.785217302   6.450041079    0   0   0
> 
> Ru       6.844051215   3.896707075   0.083664510
> 
> Ru       6.803962082   3.925582765   4.345935419
> 
> Ru       8.160944133   3.140480398   2.169878594
> 
> Ru       8.160679719   3.140892766   6.450041079    0   0   0
> 
> Ru       5.472098724   6.284364197   0.090046323
> 
> Ru       5.445173418   6.283512626   4.348352138
> 
> Ru       6.804685068   5.491581122   2.194295602
> 
> Ru       6.800629308   5.496568229   6.450041079    0   0   0
> 
> Ru       4.071317294   8.662559165   0.110981014
> 
> Ru       4.081139663   8.638147385   4.346996601
> 
> Ru       5.439541337   7.852516353   2.200433273
> 
> Ru       5.440578897   7.852243693   6.450041079    0   0   0
> 
> Ru       2.685022010  11.008754602   0.089154929
> 
> Ru       2.720793459  10.991899265   4.343967689
> 
> Ru       4.077047703  10.205591104   2.199390834
> 
> Ru       4.080528486  10.207919156   6.450041079    0   0   0
> 
> Ru       1.363042993  13.347745207   0.073583190
> 
> Ru       1.361559290  13.350430104   4.345054503
> 
> Ru       2.723577783  12.560504157   2.185933511
> 
> Ru       2.720478075  12.563594620   6.450041079    0   0   0
> 
> Ru      10.882444998   1.569152377   0.072781538
> 
> Ru      10.881496739   1.570363867   4.342648671
> 
> Ru      12.237584817   0.781437792   2.173528146
> 
> Ru      12.240930130   0.785217302   6.450041079    0   0   0
> 
> Ru       9.523726899   3.928213295   0.073805473
> 
> Ru       9.521412239   3.925515706   4.344705779
> 
> Ru      10.881229587   3.140405760   2.182553636
> 
> Ru      10.880879719   3.140892766   6.450041079    0   0   0
> 
> Ru       8.189451105   6.281486450   0.081381753
> 
> Ru       8.160703714   6.280573700   4.346822355
> 
> Ru       9.517621531   5.499394333   2.173047145
> 
> Ru       9.520829308   5.496568229   6.450041079    0   0   0
> 
> Ru       6.841663951   8.643529802   0.068313157
> 
> Ru       6.801904020   8.635893952   4.339414209
> 
> Ru       8.168141305   7.845815871   2.185333857
> 
> Ru       8.160778897   7.852243693   6.450041079    0   0   0
> 
> Ru       5.433547125  10.992149835   0.049127076
> 
> Ru       5.442657302  10.995054115   4.340836317
> 
> Ru       6.815744098  10.204943141   2.198574971
> 
> Ru       6.800728486  10.207919156   6.450041079    0   0   0
> 
> Ru       4.079480921  13.360641882   0.078153880
> 
> Ru       4.080494286  13.349362578   4.343090628
> 
> Ru       5.440940622  12.563860374   2.187844380
> 
> Ru       5.440678075  12.563594620   6.450041079    0   0   0
> 
> Ru      13.604344342   1.565286819   0.072478575
> 
> Ru      13.601163563   1.568664789   4.341371157
> 
> Ru      14.966982409   0.780981459   2.171507067
> 
> Ru      14.961130130   0.785217302   6.450041079    0   0   0
> 
> Ru      12.241120605   3.924345358   0.072554514
> 
> Ru      12.241744039   3.923837130   4.343597181
> 
> Ru      13.606742641   3.142557639   2.175631341
> 
> Ru      13.601079719   3.140892766   6.450041079    0   0   0
> 
> Ru      10.884351321   6.278690027   0.072299677
> 
> Ru      10.879668506   6.281316628   4.344298574
> 
> Ru      12.243274378   5.496483653   2.180453775
> 
> Ru      12.241029308   5.496568229   6.450041079    0   0   0
> 
> Ru       9.531759423   8.633513554   0.076632767
> 
> Ru       9.520456632   8.639518177   4.346293156
> 
> Ru      10.881698865   7.856614979   2.176720077
> 
> Ru      10.880978897   7.852243693   6.450041079    0   0   0
> 
> Ru       8.195939103  11.007704289   0.083611578
> 
> Ru       8.161520470  10.993102063   4.345293546
> 
> Ru       9.520699512  10.210057797   2.178590684
> 
> Ru       9.520928486  10.207919156   6.450041079    0   0   0
> 
> Ru       6.804866616  13.357686743   0.079162526
> 
> Ru       6.801935753  13.349151958   4.343390811
> 
> Ru       8.155982796  12.556965776   2.185900158
> 
> Ru       8.160878075  12.563594620   6.450041079    0   0   0
> 
> H   3.668277   3.396562  -1.870805
> 
> K_POINTS automatic
> 
>   2 2 1   1 1 0

********************************************************
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********************************************************

   Giuseppe Mattioli                            
   CNR - ISTITUTO DI STRUTTURA DELLA MATERIA   
   v. Salaria Km 29,300 - C.P. 10                
   I 00015 - Monterotondo Stazione (RM)          
   Tel + 39 06 90672836 - Fax +39 06 90672316    
   E-mail: <giuseppe.mattioli at ism.cnr.it>
   ResearcherID: F-6308-2012




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