Quickstep: SCF Energy increasing after few outer-SCF cycles

Sharma SRK Chaitanya Yamijala sharma... at gmail.com
Wed Aug 21 13:54:12 UTC 2013


Dear all CP2K users,

I am trying to optimize a Graphene Quantum Dot using BLYP-DFT-D3/DZVP 
method as implemented in CP2K. While optimizing I have observed that,  SCF 
energy is decreasing (i.e. becoming more negative) at the beginning of the 
run, but after few outer-SCF loops, the energy starts increasing and the 
increment is going on and on if I am leaving the system to run. 

Also, I have observed that the inner-SCF energy has reached a convergence 
(for this system) value  of ~ 10^(-5) after 2 outer-SCF cycles  (where my 
EPS_SCF is 1.0E-6) and after the beginning of the 3rd outer-SCF tolerance 
has increased to a value of ~ 10^(-3). 

I would like to get your suggestions on any way to avoid this convergence 
issue. The input file and the output file (just before and after the 2nd 
outer-SCF) are given below (hopping they may be help you in suggesting).

Thank you all,
Sincerely,
Sharma.

P.S: I have checked in the mailing list but I couldn't exactly found any 
post on this issue (though there are on BOMD-energy increment etc.)

*Input_file:*

&FORCE_EVAL

  METHOD Quickstep

  &DFT

    CHARGE = 0 
    MULTIPLICITY = 2
    LSD # for odd number of electrons and specifying this keyword itself 
enforces for spin-polarized calculations

    BASIS_SET_FILE_NAME  BASIS_MOLOPT
    POTENTIAL_FILE_NAME  GTH_POTENTIALS

    &MGRID
      CUTOFF 320
      NGRIDS 5 
      REL_CUTOFF 40
    &END MGRID

    &QS
      METHOD GPW
      EPS_DEFAULT 1.0E-10
    &END QS

    &SCF

      SCF_GUESS RESTART
      EPS_SCF 1.0E-6
      MAX_SCF 100

      &OUTER_SCF
        EPS_SCF 1.0E-6
        MAX_SCF 500
      &END

      &OT
        MINIMIZER CG
        PRECONDITIONER FULL_ALL
        ENERGY_GAP 0.001
        STEPSIZE 0.05
      &END

    &END SCF

    &XC

      &XC_FUNCTIONAL BLYP 
      &END XC_FUNCTIONAL

      &XC_GRID
        XC_DERIV  SPLINE2
        XC_SMOOTH_RHO NN50
      &END XC_GRID

      &vdW_POTENTIAL

        DISPERSION_FUNCTIONAL PAIR_POTENTIAL # POTENTIAL_TYPE is alias to 
DISPERSION_FUNCTIONAL
 

        &PAIR_POTENTIAL
          TYPE DFTD3
          PARAMETER_FILE_NAME  dftd3.dat 
          REFERENCE_FUNCTIONAL BLYP 
        &END PAIR_POTENTIAL

      &END vdW_POTENTIAL

    &END XC

    &POISSON
      POISSON_SOLVER WAVELET
      PERIODIC NONE
    &END POISSON

  &END DFT

  &SUBSYS

    &CELL 
      ABC 38.0 38.0 38.0
      ALPHA_BETA_GAMMA  90.0 90.0 90.00
      PERIODIC NONE
    &END CELL

    &TOPOLOGY
      &CENTER_COORDINATES
      &END
    &END

    &COORD
     @INCLUDE gqd_270.xyz
    &END COORD

    &KIND H
      BASIS_SET DZVP-MOLOPT-SR-GTH
      POTENTIAL GTH-BLYP-q1
    &END KIND

    &KIND C
      BASIS_SET DZVP-MOLOPT-SR-GTH
      POTENTIAL GTH-BLYP-q4
    &END KIND

    &KIND N
      BASIS_SET DZVP-MOLOPT-SR-GTH
      POTENTIAL GTH-BLYP-q5
    &END KIND

  &END SUBSYS

&END FORCE_EVAL

&GLOBAL
  PROJECT au20_tetra_on_n-gqd
  RUN_TYPE GEO_OPT 
  PRINT_LEVEL MEDIUM
&END GLOBAL

&MOTION
  &GEO_OPT
    OPTIMIZER BFGS 
    MAX_ITER   5000
    MAX_FORCE  1.00D-4 
    TYPE MINIMIZATION
  &END

&END MOTION

###########################################################################################################################
*
*
*OUTPUT-FILE:*


    98 OT LS       0.54E-01    6.9                    -1982.8376246687

  Trace(PS):                                 1174.9999638412
  Electronic density on regular grids:      -1174.9999638398        
0.0000361602
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.0000360489
  Total charge density g-space grids:           0.0000360489

    99 OT CG       0.54E-01   12.3     0.00000845     -1982.8383595833 
-7.61E-05

  Trace(PS):                                 1174.9999635922
  Electronic density on regular grids:      -1174.9999635907        
0.0000364093
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.0000362980
  Total charge density g-space grids:           0.0000362980

   100 OT LS       0.22E+00    6.9                    -1982.8383813757

  *** SCF run NOT converged ***


  Electronic density on regular grids:      -1174.9999635907        
0.0000364093
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.0000362980
  Total charge density g-space grids:           0.0000362980

  Overlap energy of the core charge distribution:               
0.00005046108667
  Self energy of the core charge distribution:              
-4271.91259980407449
  Core Hamiltonian energy:                                   
1351.88408937624945
  Hartree energy:                                            
1448.17384258600623
  Exchange-correlation energy:                               
-510.06161737575133
  Dispersion energy:                                           
-0.92214661917833

  Total energy:                                             
-1982.83838137566136

  outer SCF iter =    3 RMS gradient =   0.84E-05 energy =      
-1982.8383813757

  ----------------------------------- OT 
---------------------------------------

  Allowing for rotations:  F
  Optimizing orbital energies:  F
  Minimizer      : CG                  : conjugate gradient
  Preconditioner : FULL_ALL            : diagonalization, state selective
  Precond_solver : DEFAULT
  Line search    : 2PNT                : 2 energies, one gradient
  stepsize       :    0.05000000
  energy_gap     :    0.00100000

  eps_taylor     :   0.10000E-15
  max_taylor     :             4

  mixed_precision    : F

  ----------------------------------- OT 
---------------------------------------

  Step     Update method      Time    Convergence         Total energy    
Change
  
------------------------------------------------------------------------------

  Trace(PS):                                 1174.9999628452
  Electronic density on regular grids:      -1174.9999628438        
0.0000371562
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.0000370449
  Total charge density g-space grids:           0.0000370449

     1 OT CG       0.50E-01   24.7     0.00073898     -1982.8383578477  
1.74E-06

  Trace(PS):                                 1174.6089204778
  Electronic density on regular grids:      -1174.6089204763        
0.3910795237
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.3910794124
  Total charge density g-space grids:           0.3910794124

     2 OT LS       0.16E-01    6.8                    -1982.7669389193

  Trace(PS):                                 1174.8781005916
  Electronic density on regular grids:      -1174.8781005901        
0.1218994099
  Core density on regular grids:             1174.9999998887       
-0.0000001113
  Total charge density on r-space grids:        0.1218992986
  Total charge density g-space grids:           0.1218992986

     3 OT CG       0.16E-01   12.3     0.00075231     -1982.7595972134  
7.88E-02





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