[CP2K-user] [CP2K:13977] CP2K M06-2X water energy lower vs Other program

Leopold Talirz leopol... at gmail.com
Thu Apr 8 19:10:11 UTC 2021


Just to follow up on this thread, since I came across it as well:
There has both been a fix for mGGA forces with GAPW and all-electron [1] as 
well as a fix for the TPSS implementation with LDS [2] (by switching to 
libxc).

Both fixes are released in cp2k 8.1

[1] https://github.com/cp2k/cp2k/pull/1169
[2] https://github.com/cp2k/cp2k/pull/1184



On Thursday, 1 October 2020 at 19:41:02 UTC+2 mdsi... at gmail.com wrote:

> Hi,
>
> Are there any ideas for the wrong numbers using GAPW?  I would like to use 
> mGGAs for real time propagation with all electron.
>
> Thanks!
>
> On Friday, September 25, 2020 at 9:00:05 AM UTC-4 Matthias Krack wrote:
>
>> Hi
>>
>>  
>>
>> wrong numbers are obtained for mGGAs (like M06-2X) with GAPW, which is 
>> mandatory for all-electron calculations. The mGGA results, including 
>> M06-2X, using GPW are correct:
>>
>>  
>>
>> DEBUG|======================== BEGIN OF SUMMARY 
>> ===============================
>>
>> DEBUG| Atom  Coordinate   f(numerical)   f(analytical)   Difference   
>> Error [%]
>>
>> DEBUG|    1      x         -0.00000000     -0.00000000  
>> -0.00000000           -
>>
>> DEBUG|    1      y         -0.00000000     -0.00000003  
>> -0.00000003           -
>>
>> DEBUG|    1      z         -0.01487972     -0.01487506   
>> 0.00000465        0.03
>>
>> DEBUG|    2      x          0.00000000      0.00000000   
>> 0.00000000           -
>>
>> DEBUG|    2      y         -0.00408127     -0.00408117   
>> 0.00000009        0.00
>>
>> DEBUG|    2      z          0.00661315      0.00661293  
>> -0.00000023        0.00
>>
>> DEBUG|    3      x          0.00000000      0.00000000   
>> 0.00000000           -
>>
>> DEBUG|    3      y          0.00408126      0.00408120  
>> -0.00000006        0.00
>>
>> DEBUG|    3      z          0.00661315      0.00661298  
>> -0.00000017        0.00
>>
>> DEBUG| Sum of differences:                               0.00000524
>>
>> DEBUG|======================== END OF SUMMARY 
>> =================================
>>
>>  
>>
>> HTH
>>
>>  
>>
>> Matthias
>>
>>  
>>
>> *From:* c... at googlegroups.com <c... at googlegroups.com> *On Behalf Of *
>> mdsi... at gmail.com
>> *Sent:* Freitag, 25. September 2020 14:03
>> *To:* cp2k <c... at googlegroups.com>
>> *Subject:* Re: [CP2K:13977] CP2K M06-2X water energy lower vs Other 
>> program
>>
>>  
>>
>> I'm guessing I probably shouldn't use the M06-2X functional for anything 
>> right now or at least until why the energy discrepancy is figured out in 
>> the meta functionals?
>>
>> On Thursday, September 24, 2020 at 1:13:45 PM UTC-4 Matthias Krack wrote:
>>
>> Hi Jürg
>>
>>  
>>
>> The debug run fails also with
>>
>>  
>>
>> &XC_FUNCTIONAL TPSS
>>
>> &END XC_FUNCTIONAL
>>
>>  
>>
>> DEBUG| Atom  Coordinate   f(numerical)   f(analytical)   Difference   
>> Error [%]
>>
>> DEBUG|    1      x         -0.00000225     -0.00062077  -0.00061852      
>> -99.64
>>
>> DEBUG|    1      y         -0.00000225     -0.00050477  -0.00050253      
>> -99.55
>>
>> DEBUG|    1      z          0.01173212      0.01219262   0.00046050       
>> -3.78
>>
>>  
>>
>> Matthias
>>
>>  
>>
>> -----Original Message-----
>> From: c... at googlegroups.com <c... at googlegroups.com> On Behalf Of 
>> h... at chem.uzh.ch
>> Sent: Donnerstag, 24. September 2020 18:55
>> To: c... at googlegroups.com
>> Subject: RE: [CP2K:13972] CP2K M06-2X water energy lower vs Other program
>>
>>  
>>
>> Hi Matthias
>>
>>  
>>
>> thank you. Can I ask you to run the same debug run for M06L and TPSS, two 
>> other meta functionals?
>>
>>  
>>
>> Juerg
>>
>> --------------------------------------------------------------
>>
>> Juerg Hutter                         Phone : ++41 44 635 4491 
>> <+41%2044%20635%2044%2091>
>>
>> Institut für Chemie C                FAX   : ++41 44 635 6838 
>> <+41%2044%20635%2068%2038>
>>
>> Universität Zürich                   E-mail: h... at chem.uzh.ch
>>
>> Winterthurerstrasse 190
>>
>> CH-8057 Zürich, Switzerland
>>
>> ---------------------------------------------------------------
>>
>>  
>>
>> ----... at googlegroups.com wrote: -----
>>
>> To: "'c... at googlegroups.com'" <c... at googlegroups.com>
>>
>> From: "Krack Matthias (PSI)" 
>>
>> Sent by: c... at googlegroups.com
>>
>> Date: 09/24/2020 06:49PM
>>
>> Subject: RE: [CP2K:13971] CP2K M06-2X water energy lower vs Other program
>>
>>  
>>
>>        
>>
>>  Hi Jürg
>>
>>   
>>
>>  Unfortunately, there seems to be more than the 5d/6d difference when 
>> using the M06-2X functional. A comparison of the H2O structures relaxed 
>> with 6-31G** using BLYP, HF, B3LYP, and M06-2X reveals indeed a much larger 
>> difference for M06-2X:
>>
>>   
>>
>>       H2O/6-31G**
>>
>>          CCCBDB
>>
>>             CP2K
>>
>>       BLYP       
>>
>>      -76.398885
>>
>>       -76.396840
>>
>>       HF         
>>
>>      -76.023615
>>
>>       -76.023047
>>
>>       B3LYP      
>>
>>      -76.419737
>>
>>       -76.418114
>>
>>       M06-2X      
>>
>>      -76.383939
>>
>>       -76.378
>>
>>       
>>
>>  Moreover, the GEO_OPT run with M06-2X shows difference in the OH bonds 
>> which indicates wrong forces and indeed a DEBUG run reveals that there 
>> exists a problem related to M06-2X using the XC section as suggested:
>>
>>   
>>
>>  DEBUG| Atom  Coordinate   f(numerical)   f(analytical)   Difference   
>> Error [%]
>>
>> DEBUG|    1      x          0.00000768     -0.00011877  -0.00012645     
>> -106.47
>>
>> DEBUG|    1      y         -0.00006753      0.00169850   0.00176603     
>> -103.98
>>
>> DEBUG|    1      z         -0.00096067     -0.00096000   
>> 0.00000066        0.07
>>
>> application called MPI_Abort(MPI_COMM_WORLD, 1) - process 0
>>
>>   
>>
>>
>>  *******************************************************************************
>>
>> *   
>> ___                                                                       *
>>
>> *  /   
>> \                                                                      *
>>
>> * [ABORT]      A mismatch between analytical and numerical forces has 
>> been    *
>>
>> *  \___/       detected. Check the implementation of the analytical 
>> force     *
>>
>> *    |      
>>                            calculation                            *
>>
>> *  
>> O/|                                                                        *
>>
>> * /| 
>> |                                                                        *
>>
>> * / \                    
>>                                     cp2k_debug.F:318 *
>>
>>
>> *******************************************************************************
>>
>>   
>>
>>  A debug run with B3LYP works fine with errors of only 0.01%.
>>
>>   
>>
>>  So there is either an input error (&XC section with M06-2X) or a bug in 
>> CP2K (or libxc).
>>
>>   
>>
>>  Best regards
>>
>>   
>>
>>  Matthias
>>
>>   
>>
>>  -----Original Message-----
>>
>> From: c... at googlegroups.com <c... at googlegroups.com> On Behalf Of 
>> h... at chem.uzh.ch
>>
>> Sent: Donnerstag, 24. September 2020 17:53
>>
>> To: c... at googlegroups.com
>>
>> Subject: Re: [CP2K:13969] CP2K M06-2X water energy lower vs Other program
>>
>>   
>>
>>  Hi
>>
>>   
>>
>>  so as I said, the basis sets are different and that makes the results 
>> different.
>>
>>   
>>
>>  JH
>>
>> --------------------------------------------------------------
>>
>> Juerg Hutter                         Phone : ++41 44 635 4491 
>> <+41%2044%20635%2044%2091>
>>
>> Institut für Chemie C                FAX   : ++41 44 635 6838 
>> <+41%2044%20635%2068%2038>
>>
>> Universität Zürich                   E-mail:  h... at chem.uzh.ch
>>
>> Winterthurerstrasse 190
>>
>> CH-8057 Zürich, Switzerland
>>
>> ---------------------------------------------------------------
>>
>>   
>>
>>  ----... at googlegroups.com wrote: -----
>>
>> To: "cp2k" <c... at googlegroups.com>
>>
>> From: "mdsi... at gmail.com" 
>>
>>  Sent by: c... at googlegroups.com
>>
>> Date: 09/24/2020 05:17PM
>>
>> Subject: Re: [CP2K:13969] CP2K M06-2X water energy lower vs Other program
>>
>>   
>>
>>  Hi Prof Hutter,
>>
>>   
>>
>>  Here's from CP2K
>>
>> Total number of            - Atomic 
>> kinds:                                   2
>>
>>                               - 
>> Atoms:                                          3
>>
>>                               - Shell 
>> sets:                                    10
>>
>>                               - 
>> Shells:                                        12
>>
>>                               - Primitive Cartesian 
>> functions:                 21
>>
>>                               - Cartesian basis 
>> functions:                     25
>>
>>                               - Spherical basis 
>> functions:                     24
>>
>>   
>>
>>  This is from Gaussian
>>
>> Standard basis: 6-31G(d,p) (6D, 7F)
>>
>>      25 basis functions,    42 primitive gaussians,    25 cartesian basis 
>> functions
>>
>> On Thursday, September 24, 2020 at 10:27:08 AM UTC-4 jgh wrote:
>>
>> Hi
>>
>> check the number of basis functions. Part or hopefully all of the energy 
>> difference is from the (6d) default in Gaussian. 
>>
>>  CP2K uses spherical functions only. 
>>
>>   
>>
>>  regards 
>>
>>   
>>
>>  JH
>>
>> -------------------------------------------------------------- 
>>
>>  Juerg Hutter                         Phone : ++41 44 635 4491 
>> <+41%2044%20635%2044%2091> 
>>
>>  Institut für Chemie C                FAX   : ++41 44 635 6838 
>> <+41%2044%20635%2068%2038> 
>>
>>  Universität Zürich                   E-mail:  h... at chem.uzh.ch 
>>
>>  Winterthurerstrasse 190
>>
>> CH-8057 Zürich, Switzerland
>>
>> --------------------------------------------------------------- 
>>
>>   
>>
>>  -----c... at googlegroups.com wrote: -----
>>
>> To: "cp2k" <c... at googlegroups.com>
>>
>> From: "mdsi... at gmail.com"  
>>
>>  Sent by: c... at googlegroups.com
>>
>> Date: 09/24/2020 04:00PM
>>
>> Subject: [CP2K:13967] CP2K M06-2X water energy lower vs Other program 
>>
>>   
>>
>>  Hello, 
>>
>>   
>>
>>  The water energy at the M06-2X/6-31G** level is quite different when 
>> compared to Gaussian and the CCCBDB. 
>>
>>   
>>
>>  Gaussian: -76.3831231205 Ha (#n M062X/6-31G** NoSymm SCF=(XQC, 
>> maxconventionalcycles=30) Int=UltraFine SP) 
>>
>>  CCCBDB:   -76.383939 Ha (
>> https://cccbdb.nist.gov/energy3x.asp?method=58&basis=3&charge=0) 
>>
>>  CP2K:        -76.401243254272231Ha 
>>
>>   
>>
>>  Anyone have any ideas on what settings need to be modified or can CP2K 
>> match that energy? 
>>
>>   
>>
>>  My CP2K input: 
>>
>>
>>  ****************************************************************************
>>
>> @SET COORD_FILENAME water.xyz 
>>
>>   
>>
>>  &GLOBAL 
>>
>>          PROJECT H2O_Eng 
>>
>>          RUN_TYPE ENERGY 
>>
>>          PRINT_LEVEL LOW
>>
>> &END GLOBAL 
>>
>>   
>>
>>  &FORCE_EVAL 
>>
>>          METHOD Quickstep 
>>
>>   
>>
>>          &DFT 
>>
>>                  BASIS_SET_FILE_NAME EMSL_BASIS_SETS  
>>
>>                  POTENTIAL_FILE_NAME POTENTIAL 
>>
>>   
>>
>>                  CHARGE 0 
>>
>>                  MULTIPLICITY 1 
>>
>>   
>>
>>                  &QS 
>>
>>                          METHOD GAPW 
>>
>>                          EPS_DEFAULT 1.0E-9 
>>
>>                          EXTRAPOLATION ASPC 
>>
>>                          MAP_CONSISTENT 
>>
>>                          EPSFIT       1.E-4 ! precision to give the 
>> extension of a hard gaussian 
>>
>>                          EPSISO       1.0E-12 
>>
>>                          EPSRHO0      1.E-8 
>>
>>                          LMAXN0       4 
>>
>>                          LMAXN1       6 
>>
>>                          ALPHA0_H     10 ! Exponent for hard compensation 
>> charge 
>>
>>              &END QS 
>>
>>   
>>
>>                  &MGRID 
>>
>>                          NGRIDS 5 
>>
>>                          CUTOFF 600 
>>
>>                          REL_CUTOFF 100 
>>
>>                  &END MGRID 
>>
>>   
>>
>>                  &SCF 
>>
>>                          MAX_SCF 50 
>>
>>                          SCF_GUESS ATOMIC 
>>
>>                          EPS_SCF 1E-8 
>>
>>                  &END SCF 
>>
>>   
>>
>>                  &POISSON 
>>
>>                          PERIODIC NONE 
>>
>>                          POISSON_SOLVER WAVELET 
>>
>>                  &END POISSON 
>>
>>   
>>
>>                  &XC 
>>
>>                          &XC_GRID 
>>
>>                                  XC_DERIV NN10_SMOOTH  
>>
>>                                  XC_SMOOTH_RHO NN10 
>>
>>                          &END XC_GRID 
>>
>>                          &XC_FUNCTIONAL 
>>
>>                                  &LIBXC 
>>
>>                                          FUNCTIONAL MGGA_C_M06_2X 
>>
>>                                  &END LIBXC 
>>
>>                                  &LIBXC 
>>
>>                                          FUNCTIONAL HYB_MGGA_X_M06_2X  
>>
>>                                  &END LIBXC 
>>
>>                          &END XC_FUNCTIONAL 
>>
>>                          &HF 
>>
>>                                  FRACTION 0.54 
>>
>>                                  &SCREENING 
>>
>>                                          EPS_SCHWARZ 1.0E-10 
>>
>>                                  &END SCREENING 
>>
>>                                  &MEMORY 
>>
>>                                          MAX_MEMORY 1000  
>>
>>                                          EPS_STORAGE_SCALING 0.1 
>>
>>                                  &END MEMORY 
>>
>>                                  &INTERACTION_POTENTIAL  
>>
>>                                          POTENTIAL_TYPE COULOMB 
>>
>>                                  &END INTERACTION_POTENTIAL 
>>
>>                          &END HF 
>>
>>                  &END XC 
>>
>>          &END DFT 
>>
>>   
>>
>>          &SUBSYS 
>>
>>                  &CELL 
>>
>>                          ABC 10.0 10.0 10.0 
>>
>>                          ALPHA_BETA_GAMMA 90.000 90.000 90.000 
>>
>>                          PERIODIC NONE 
>>
>>                  &END CELL 
>>
>>                   
>>
>>                  &TOPOLOGY 
>>
>>                          COORD_FILE_FORMAT XYZ 
>>
>>                          COORD_FILE_NAME ${COORD_FILENAME} 
>>
>>                          &CENTER_COORDINATES 
>>
>>                          &END CENTER_COORDINATES 
>>
>>                  &END TOPOLOGY 
>>
>>   
>>
>>                  &KIND H 
>>
>>                          ELEMENT        H 
>>
>>                          BASIS_SET 6-31Gxx 
>>
>>                          POTENTIAL ALL 
>>
>>                          LEBEDEV_GRID 80 
>>
>>                          RADIAL_GRID 200 
>>
>>                  &END KIND 
>>
>>   
>>
>>                  &KIND O 
>>
>>                          ELEMENT        O 
>>
>>                          BASIS_SET 6-31Gxx 
>>
>>                          POTENTIAL ALL 
>>
>>                          LEBEDEV_GRID 80 
>>
>>                          RADIAL_GRID 200 
>>
>>                  &END KIND 
>>
>>          &END SUBSYS
>>
>> &END FORCE_EVAL 
>>
>>   
>>
>>     
>>
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