[CP2K-user] [CP2K:19284] Very high RSME and RRSME in RESP charge fitting

Prateek Chowdhury prateekchowdhury1 at gmail.com
Sat Sep 30 22:49:54 UTC 2023


Hello...

I am new to cp2k. I started with geometric optimization and partial charge 
calculation of MoS2 (hexagonal) and CdS (cubic) crystals (2*2*1 supercells 
for the time being) respectively. For charge calculation, I was using RESP 
fitting method. For MoS2, the fitting was good showing sufficiently low 
RRMSE (~ 0.09 - 0.1) and RMSE (~0.00005), respectively, and the fitted data 
matched with literature too. 
Conversely, during the same exercise for CdS, inspite of achieving 
physically reasonable partial charges for both Cd (~ +2.00) and S (~ 
-2.00), the RRMSE (~ 0.98 - 0.99) and RMSE (~ 0.0008) came out to be 
extremely high. I wonder why this is happening in doing the similar 
exercise, despite using the similar PPs and Basis sets. I shall be highly 
obliged if anyone helps me out with this. I have attached my input files 
and the PPs and Basis sets used for both the cases below.

Cd (PP): GTH-PBE-q12
Cd (BS): DZVP-MOLOPT-SR-GTH-q12
S (PP): GTH-PBE-q6
S (BS): TZVP-MOLOPT-GTH-q6

Mo (PP): GTH-PBE-q14
Mo (BS): DZVP-MOLOPT-SR-GTH 
S (PP): GTH-PBE-q6 
S (BS): DZVP-MOLOPT-GTH

I am adding RESP charge printed sections for both the cases in two separate 
files too.

Thanks in advance...
Prateek.

-- 
You received this message because you are subscribed to the Google Groups "cp2k" group.
To unsubscribe from this group and stop receiving emails from it, send an email to cp2k+unsubscribe at googlegroups.com.
To view this discussion on the web visit https://groups.google.com/d/msgid/cp2k/da9368d2-4cfe-479b-bd52-dd6f007d24c5n%40googlegroups.com.
-------------- next part --------------
An HTML attachment was scrubbed...
URL: <https://lists.cp2k.org/archives/cp2k-user/attachments/20230930/336b97ce/attachment.htm>
-------------- next part --------------
  RESP       1  Mo    3.912250
  RESP       2  S    -1.727979
  RESP       3  Mo    3.469619
  RESP       4  S    -1.835246
  RESP       5  S    -1.727976
  RESP       6  S    -1.835239
  RESP       7  Mo    3.743370
  RESP       8  S    -1.694892
  RESP       9  Mo    3.469613
  RESP      10  S    -1.835240
  RESP      11  S    -1.694903
  RESP      12  S    -1.835237
  RESP      13  Mo    3.291544
  RESP      14  S    -1.639564
  RESP      15  Mo    3.297772
  RESP      16  S    -1.753063
  RESP      17  S    -1.639563
  RESP      18  S    -1.753054
  RESP      19  Mo    3.291562
  RESP      20  S    -1.639560
  RESP      21  Mo    3.200912
  RESP      22  S    -1.712775
  RESP      23  S    -1.639571
  RESP      24  S    -1.712778
  Total               0.000000

  Root-mean-square (RMS) error of RESP fit:                          7.91801E-05
  Relative root-mean-square (RRMS) error of RESP fit:                1.25106E-01
-------------- next part --------------
&GLOBAL
  PROJECT cds
  RUN_TYPE GEO_OPT
  PRINT_LEVEL LOW
&END GLOBAL

&FORCE_EVAL
  METHOD QS
  &SUBSYS
    &CELL
      ABC 11.62 11.62 5.81
    &END CELL
    &COORD
     	Cd  0.00000000  0.00000000  0.00000000
	S  1.45250000  1.45250000  1.45250000
	S  1.45250000  4.35750000  4.35750000
	S  4.35750000  1.45250000  4.35750000
	S  4.35750000  4.35750000  1.45250000
	Cd  0.00000000  2.90500000  2.90500000
	Cd  2.90500000  0.00000000  2.90500000
	Cd  2.90500000  2.90500000  0.00000000
	Cd  5.81000000  0.00000000  0.00000000
	S  7.26250000  1.45250000  1.45250000
	S  7.26250000  4.35750000  4.35750000
	S  10.16750000  1.45250000  4.35750000
	S  10.16750000  4.35750000  1.45250000
	Cd  5.81000000  2.90500000  2.90500000
	Cd  8.71500000  0.00000000  2.90500000
	Cd  8.71500000  2.90500000  0.00000000
	Cd  0.00000000  5.81000000  0.00000000
	S  1.45250000  7.26250000  1.45250000
	S  1.45250000  10.16750000  4.35750000
	S  4.35750000  7.26250000  4.35750000
	S  4.35750000  10.16750000  1.45250000
	Cd  0.00000000  8.71500000  2.90500000
	Cd  2.90500000  5.81000000  2.90500000
	Cd  2.90500000  8.71500000  0.00000000
	Cd  5.81000000  5.81000000  0.00000000
	S  7.26250000  7.26250000  1.45250000
	S  7.26250000  10.16750000  4.35750000
	S  10.16750000  7.26250000  4.35750000
	S  10.16750000  10.16750000  1.45250000
	Cd  5.81000000  8.71500000  2.90500000
	Cd  8.71500000  5.81000000  2.90500000
	Cd  8.71500000  8.71500000  0.00000000
    &END COORD

    &KIND Cd
      BASIS_SET DZVP-MOLOPT-SR-GTH-q12  
      POTENTIAL GTH-PBE-q12
    &END KIND

    &KIND S
      BASIS_SET TZVP-MOLOPT-GTH-q6
      POTENTIAL GTH-PBE-q6
    &END KIND

  &END SUBSYS

  &DFT
    BASIS_SET_FILE_NAME ./BASIS_MOLOPT.txt
    POTENTIAL_FILE_NAME ./POTENTIAL.txt
    CHARGE 0
    MULTIPLICITY 1

    &QS
      METHOD GAPW
      EPS_DEFAULT 1.0E-12
    &END QS

    &MGRID
      CUTOFF 750
      NGRIDS 4
      REL_CUTOFF 30
    &END MGRID

    &SCF
      SCF_GUESS ATOMIC
      EPS_SCF 1.0E-05
      MAX_SCF 100

      &DIAGONALIZATION T
        ALGORITHM STANDARD
      &END DIAGONALIZATION

      &MIXING T
        ALPHA 0.2
        BETA 1.5
        METHOD PULAY_MIXING
        NPULAY 5
      &END MIXING

    &END SCF

    &XC
      &XC_FUNCTIONAL PBE
      &END XC_FUNCTIONAL

      &VDW_POTENTIAL
       &PAIR_POTENTIAL
      	D3BJ_SCALING 2.0 2.0 2.0 2.0
       &END PAIR_POTENTIAL
      &END VDW_POTENTIAL

    &END XC

  &END DFT
  &PROPERTIES
   &RESP
     &SPHERE_SAMPLING
     &END
   &END RESP
   &FIT_CHARGE
   &END FIT_CHARGE
  &END PROPERTIES

&END FORCE_EVAL
&MOTION
  &GEO_OPT
    TYPE MINIMIZATION
    MAX_DR    1.0E-05
    MAX_FORCE 1.0E-05
    RMS_DR    1.0E-05    
    RMS_FORCE 1.0E-05
    MAX_ITER 250
    OPTIMIZER CG
    &CG
      MAX_STEEP_STEPS  0
      RESTART_LIMIT 9.0E-01
    &END CG
  &END GEO_OPT
  &CONSTRAINT
    &FIXED_ATOMS
      COMPONENTS_TO_FIX XYZ
      LIST 1
    &END FIXED_ATOMS
  &END CONSTRAINT
&END MOTION  
-------------- next part --------------
&GLOBAL
  PROJECT mos2
  RUN_TYPE GEO_OPT
  PRINT_LEVEL LOW
&END GLOBAL
&FORCE_EVAL
  METHOD QS
  &SUBSYS
    &CELL
      ABC 6.322 5.478 12.295
    &END CELL
    &COORD
      Mo  -0.00001580  1.82501333  3.07375000
	S  -0.00001580  1.82501333  7.71511250
	Mo  1.58050000  0.91252035  9.22125000
	S  1.58050000  0.91252035  1.56761250
	S  0.00000000  1.82498595  10.72738750
	S  1.58051581  0.91249298  4.57988750
	Mo  3.16098420  1.82501333  3.07375000
	S  3.16098420  1.82501333  7.71511250
	Mo  4.74150000  0.91252035  9.22125000
	S  4.74150000  0.91252035  1.56761250
	S  3.16100000  1.82498595  10.72738750
	S  4.74151581  0.91249298  4.57988750
	Mo  -1.58051580  4.56251963  3.07375000
	S  -1.58051580  4.56251963  7.71511250
	Mo  0.00000000  3.65002665  9.22125000
	S  0.00000000  3.65002665  1.56761250
	S  -1.58050000  4.56249225  10.72738750
	S  0.00001581  3.64999928  4.57988750
	Mo  1.58048420  4.56251963  3.07375000
	S  1.58048420  4.56251963  7.71511250
	Mo  3.16100000  3.65002665  9.22125000
	S  3.16100000  3.65002665  1.56761250
	S  1.58050000  4.56249225  10.72738750
	S  3.16101581  3.64999928  4.57988750
    &END COORD
    &KIND Mo
      BASIS_SET DZVP-MOLOPT-SR-GTH  
      POTENTIAL GTH-PBE-q14
    &END KIND
    &KIND S
      BASIS_SET DZVP-MOLOPT-GTH
      POTENTIAL GTH-PBE-q6
    &END KIND
  &END SUBSYS
  &DFT
    BASIS_SET_FILE_NAME ./BASIS_SET
    POTENTIAL_FILE_NAME ./GTH_POTENTIALS
    &QS
      EPS_DEFAULT 1.0E-7
    &END QS
    &MGRID
      CUTOFF 750
      NGRIDS 4
      REL_CUTOFF 30
    &END MGRID
    &SCF
      SCF_GUESS ATOMIC
      EPS_SCF 1.0E-05
      MAX_SCF 200
      &DIAGONALIZATION T
        ALGORITHM STANDARD
      &END DIAGONALIZATION
      &MIXING T
        ALPHA 0.5
        METHOD PULAY_MIXING
        NPULAY 5
      &END MIXING
    &END SCF
    &XC
      &XC_FUNCTIONAL PBE
      &END XC_FUNCTIONAL
    &END XC
    &DENSITY_FITTING
      GCUT 2.45
      MIN_RADIUS 0.264
      NUM_GAUSS 3
      PFACTOR 1.5
    &END DENSITY_FITTING   
  &END DFT
  &PROPERTIES
   &RESP
     &SPHERE_SAMPLING
     &END
     &PRINT
       &COORD_FIT_POINTS
       &END
      &END
   &END RESP
  &END PROPERTIES
&END FORCE_EVAL
&MOTION
  &GEO_OPT
    TYPE MINIMIZATION
    MAX_DR    1.0E-04
    MAX_FORCE 1.0E-04
    RMS_DR    1.0E-04    
    RMS_FORCE 1.0E-04
    MAX_ITER 250
    OPTIMIZER CG
    &CG
      MAX_STEEP_STEPS  0
      RESTART_LIMIT 9.0E-01
    &END CG
  &END GEO_OPT
  &CONSTRAINT
    &FIXED_ATOMS
      COMPONENTS_TO_FIX XYZ
      LIST 1
    &END FIXED_ATOMS
  &END CONSTRAINT
&END MOTION  
-------------- next part --------------
 RESP       1  Cd   -2.336000
  RESP       2  S     2.338112
  RESP       3  S     2.333793
  RESP       4  S     2.334640
  RESP       5  S     2.336156
  RESP       6  Cd   -2.340249
  RESP       7  Cd   -2.335453
  RESP       8  Cd   -2.336062
  RESP       9  Cd   -2.334731
  RESP      10  S     2.339209
  RESP      11  S     2.337037
  RESP      12  S     2.342364
  RESP      13  S     2.339660
  RESP      14  Cd   -2.337034
  RESP      15  Cd   -2.336513
  RESP      16  Cd   -2.341948
  RESP      17  Cd   -2.334191
  RESP      18  S     2.327352
  RESP      19  S     2.330490
  RESP      20  S     2.321137
  RESP      21  S     2.331393
  RESP      22  Cd   -2.330442
  RESP      23  Cd   -2.329192
  RESP      24  Cd   -2.324471
  RESP      25  Cd   -2.330641
  RESP      26  S     2.328812
  RESP      27  S     2.331433
  RESP      28  S     2.336403
  RESP      29  S     2.332194
  RESP      30  Cd   -2.325088
  RESP      31  Cd   -2.335544
  RESP      32  Cd   -2.332626
  Total               0.000000

  Root-mean-square (RMS) error of RESP fit:                          4.20508E-04
  Relative root-mean-square (RRMS) error of RESP fit:                9.81835E-01


More information about the CP2K-user mailing list