[CP2K-user] [CP2K:13974] CP2K M06-2X water energy lower vs Other program

Krack Matthias (PSI) matthi... at psi.ch
Thu Sep 24 17:54:56 UTC 2020


Hi Lucas

Indeed, the integral calculation is performed using Cartesian Gaussian functions in CP2K as shown in the initial printout, since this representation allows for efficient recurrence relations, but the integral matrix blocks are then transformed to spherical Gaussian functions. They are also properly normalized in the same step. Thus all operator matrices like the Kohn-Sham matrix, the overlap matrix, and the wavefunctions (MOs) are represented using spherical Gaussian functions. This representation is also used by the wavefunction optimization (SCF) and determines the available degrees of freedom for the solver during the optimization which causes eventually the difference between a spherical and a Cartesian Gaussian basis set.

HTH

Matthias

From: cp... at googlegroups.com <cp... at googlegroups.com> On Behalf Of Lucas Lodeiro
Sent: Donnerstag, 24. September 2020 19:20
To: cp... at googlegroups.com
Subject: Re: [CP2K:13974] CP2K M06-2X water energy lower vs Other program

Hello Professor Hutter,

I am a little confused about the orbitals that uses CP2K. You and the CP2K paper mention that only spherical functions are used, but in the output (with the same input of the first message, justo with print_level medium) shows that 6 d functions are used for oxygen. CP2K internally transforms those 6 cartesian functions in the spherical ones? There is another "change" respect the ATOMIC KIND INFORMATION printed in the output?

Regards - Lucas Lodeiro

******************************************************************************************************************
 ATOMIC KIND INFORMATION

  1. Atomic kind: O                                     Number of atoms:       1

     Orbital Basis Set                                                   6-31Gxx

       Number of orbital shell sets:                                           4
       Number of orbital shells:                                               6
       Number of primitive Cartesian functions:                               11
       Number of Cartesian basis functions:                                   15
       Number of spherical basis functions:                                   14
       Norm type:                                                              2

       Normalised Cartesian orbitals:

                        Set   Shell   Orbital            Exponent    Coefficient

                          1       1    1s             5484.671700       0.831735
                                                       825.234950       1.530807
                                                       188.046960       2.477149
                                                        52.964500       3.256280
                                                        16.897570       2.792894
                                                         5.799635       0.954938

                          2       1    1s               15.539616      -0.617934
                                                         3.599934      -0.275721
                                                         1.013762       0.814208

                          2       2    2px              15.539616       3.116946
                                                         3.599934       2.401437
                                                         1.013762       1.054361
                          2       2    2py              15.539616       3.116946
                                                         3.599934       2.401437
                                                         1.013762       1.054361
                          2       2    2pz              15.539616       3.116946
                                                         3.599934       2.401437
                                                         1.013762       1.054361

                          3       1    1s                0.270006       0.266956

                          3       2    2px               0.270006       0.277432
                          3       2    2py               0.270006       0.277432
                          3       2    2pz               0.270006       0.277432

                          4       1    1dx2              0.800000       1.113825
                          4       1    1dxy              0.800000       1.929201
                          4       1    1dxz              0.800000       1.929201
                          4       1    1dy2              0.800000       1.113825
                          4       1    1dyz              0.800000       1.929201
                          4       1    1dz2              0.800000       1.113825

     The atoms of this atomic kind are PAW atoms (GAPW):
       Hard Gaussian function radius:                                      1.512
       Rho0 radius:                                                        1.512
       Maximum GTO radius used for PAW projector construction:            24.566

     GAPW Soft Basis Set                                            6-31Gxx_soft

       Number of orbital shell sets:                                           4
       Number of orbital shells:                                               6
       Number of primitive Cartesian functions:                                4
       Number of Cartesian basis functions:                                   15
       Number of spherical basis functions:                                   14
       Norm type:                                                              2

       Normalised Cartesian orbitals:

                        Set   Shell   Orbital            Exponent    Coefficient

                          1       1    1s

                          2       1    1s                3.599934      -0.275721
                                                         1.013762       0.814208

                          2       2    2px               3.599934       2.401437
                                                         1.013762       1.054361
                          2       2    2py               3.599934       2.401437
                                                         1.013762       1.054361
                          2       2    2pz               3.599934       2.401437
                                                         1.013762       1.054361

                          3       1    1s                0.270006       0.266956

                          3       2    2px               0.270006       0.277432
                          3       2    2py               0.270006       0.277432
                          3       2    2pz               0.270006       0.277432

                          4       1    1dx2              0.800000       1.113825
                          4       1    1dxy              0.800000       1.929201
                          4       1    1dxz              0.800000       1.929201
                          4       1    1dy2              0.800000       1.113825
                          4       1    1dyz              0.800000       1.929201
                          4       1    1dz2              0.800000       1.113825

     AE Potential information for                                            ALL

       Description:                                       All-electron potential
                                          Krack, Parrinello, PCCP 2, 2105 (2000)

       Gaussian exponent of the core charge distribution:               8.154466
       Electronic configuration (s p d ...):                           4   4   0

  2. Atomic kind: H                                     Number of atoms:       2

     Orbital Basis Set                                                   6-31Gxx

       Number of orbital shell sets:                                           3
       Number of orbital shells:                                               3
       Number of primitive Cartesian functions:                                5
       Number of Cartesian basis functions:                                    5
       Number of spherical basis functions:                                    5
       Norm type:                                                              2

       Normalised Cartesian orbitals:

                        Set   Shell   Orbital            Exponent    Coefficient

                          1       1    1s               18.731137       0.214935
                                                         2.825394       0.364571
                                                         0.640122       0.415051

                          2       1    1s                0.161278       0.181381

                          3       1    1px               1.100000       1.605761
                          3       1    1py               1.100000       1.605761
                          3       1    1pz               1.100000       1.605761

     The atoms of this atomic kind are PAW atoms (GAPW):
       Hard Gaussian function radius:                                      1.200
       Rho0 radius:                                                        1.200
       Maximum GTO radius used for PAW projector construction:            24.566

     GAPW Soft Basis Set                                            6-31Gxx_soft

       Number of orbital shell sets:                                           3
       Number of orbital shells:                                               3
       Number of primitive Cartesian functions:                                4
       Number of Cartesian basis functions:                                    5
       Number of spherical basis functions:                                    5
       Norm type:                                                              2

       Normalised Cartesian orbitals:

                        Set   Shell   Orbital            Exponent    Coefficient

                          1       1    1s                2.825394       0.364571
                                                         0.640122       0.415051

                          2       1    1s                0.161278       0.181381

                          3       1    1px               1.100000       1.605761
                          3       1    1py               1.100000       1.605761
                          3       1    1pz               1.100000       1.605761

     AE Potential information for                                            ALL

       Description:                                       All-electron potential
                                          Krack, Parrinello, PCCP 2, 2105 (2000)

       Gaussian exponent of the core charge distribution:              12.500000
       Electronic configuration (s p d ...):                           1   0   0


 MOLECULE KIND INFORMATION


 All atoms are their own molecule, skipping detailed information


 TOTAL NUMBERS AND MAXIMUM NUMBERS

  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

  Maximum angular momentum of the orbital basis functions:                     2
******************************************************************************************************************

El jue., 24 sept. 2020 a las 11:27, <hut... at chem.uzh.ch<mailto:hut... at chem.uzh.ch>> escribió:
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
Institut für Chemie C                FAX   : ++41 44 635 6838
Universität Zürich                   E-mail: hut... at chem.uzh.ch<mailto:hut... at chem.uzh.ch>
Winterthurerstrasse 190
CH-8057 Zürich, Switzerland
---------------------------------------------------------------

-----cp... at googlegroups.com<mailto:cp... at googlegroups.com> wrote: -----
To: "cp2k" <cp... at googlegroups.com<mailto:cp... at googlegroups.com>>
From: "mdsi... at gmail.com<mailto:mdsi... at gmail.com>"
Sent by: cp... at googlegroups.com<mailto:cp... 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<http://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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