problem converging molecule in doublet state

garold g.murd... at gmail.com
Fri Apr 8 03:03:30 UTC 2011


Dear CP2K Community,

I am attempting to calculate the energy of a molecule (dicarboyxlate
anion with a lithium cation; net charge is zero) in its doublet
state.  I have tried using both restricted and unrestricted formalisms
(LSD and ROKS, respectively).  However, I cannot get the SCF to
converge with either.  I have been using both B3LYP and BLYP and
various basis sets.  Ideally, I would prefer to use B3LYP/GAPW/6-31+G*
but have been unable to obtain convergence even with BLYP/GAPW/6-31G*
(no diffuse functions) or BLYP/GPW/DZVP-MOLOPT-SR-GTH (my original
assumption was that diffuse functions were source of the problem).
The input for my preferred method/basis set is below and the output is
attached.  Please let me know if you have any suggestions.  Thank you
in advance.

Note that I am using a recent tested version of cp2k compiled with
libint.  Both BLYP/ and B3LYP/GAPW/6-31+G* work well for the closed-
shell, singlet version of this system (e.g., with one electron added,
net charge of -1, same geometry).  However, a preconditioner (OT/
OUTER_SCF option) does not seem to work well for this system so I am
not using it.

Best regards,
Garold Murdachaew

ps: Input file (gzipped output file is attached):

&FORCE_EVAL
  METHOD Quickstep
  &DFT
    LSD
    CHARGE 0
    MULTIPLICITY 2
    BASIS_SET_FILE_NAME ../EMSL_BASIS_SETS_mine
    POTENTIAL_FILE_NAME ../POTENTIAL
    &MGRID
      CUTOFF 280
      NGRIDS 5
    &END MGRID
    &QS
      METHOD GAPW
    &END QS
    &POISSON
      PERIODIC NONE
      PSOLVER MT
    &END
    &SCF
      SCF_GUESS ATOMIC
      EPS_SCF 1.0E-7
      MAX_SCF 20
!     &OUTER_SCF
!       EPS_SCF 1.0E-7
!       MAX_SCF 20
!     &END
!     &OT
!       PRECONDITIONER FULL_ALL
!     &END
    &END SCF
    &XC
      &XC_FUNCTIONAL
       &LYP
         SCALE_C 0.81
       &END
       &BECKE88
         SCALE_X 0.72
       &END
       &VWN
         FUNCTIONAL_TYPE VWN3
         SCALE_C 0.19
       &END
       &XALPHA
         SCALE_X 0.08
       &END
      &END XC_FUNCTIONAL
      &HF
        &SCREENING
          EPS_SCHWARZ 1.0E-10
        &END
        &MEMORY
          MAX_MEMORY 1200
        &END
        FRACTION 0.20
      &END
    &END XC
  &END DFT
  &SUBSYS
    &CELL
      ABC 20.0 20.0 20.0
      PERIODIC NONE
    &END CELL
    &COORD
 C    -0.793023    -0.703538     0.527367
 C    -0.046767    -0.838845    -0.834379
 C    -0.109334     0.381305    -1.793731
 O    -0.533605     0.203716    -2.940264
 C     0.080655    -0.434112     1.783207
 O    -0.014088    -1.209796     2.739982
 O     0.835715     0.609771     1.736225
 O     0.313892     1.501426    -1.316006
 H    -1.529788     0.107036     0.458189
 H    -1.351096    -1.620668     0.723529
 H     1.012459    -1.057227    -0.647331
 H    -0.452088    -1.690968    -1.382698
Li     0.909030     1.669426     0.332287
    &END COORD
    &KIND C
      BASIS_SET 6-31+Gx
      POTENTIAL ALL
    &END KIND
    &KIND O
      BASIS_SET 6-31+Gx
      POTENTIAL ALL
    &END KIND
    &KIND H
      BASIS_SET 6-31Gx
      POTENTIAL ALL
    &END KIND
    &KIND Li
      BASIS_SET 6-31+Gx
      POTENTIAL ALL
    &END KIND
  &END SUBSYS
&END FORCE_EVAL
&GLOBAL
  PROJECT d_m
  PRINT_LEVEL MEDIUM
&END GLOBAL

pps: I constructed the 6-31+G* basis set simply by adding the diffuse
functions to C, O, and Li, the basis set file is attached.


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