[CP2K-user] [CP2K:21699] Discrepancy in using Range-Separated Hybrid Functional with D4 Correction

Lim Jia Yang limjiayang.ljy at gmail.com
Tue Jul 29 12:53:38 UTC 2025


Dear CP2K community,

CP2K version 2025.1, ORCA version 6.1.0
I am doing benchmarking on vertical detachment energy. Both functionals 
used are from Libxc for calculations in ORCA and CP2K.

First method: LC-ωPBE+D3BJ(2016)
Second method: LC-ωPBE08+D4

The first method gives similar values with a ~0.0002 eV difference between 
ORCA and CP2K. The second method shows differences of ~0.024 eV, with CP2K 
being lower.

Any advice is really appreciated. I hope I didn't make some mistakes in the 
input.

Attached are the CP2K input files for both methods. The output file for the 
second method shows "POWELL| Error in trust region". The same error appears 
when D4 correction is removed.

ORCA input line for the first method:
! D3BJ aug-cc-pVTZ TightSCF DEFGRID3
%method
        method dft
        functional hyb_gga_xc_lc_wpbe
        D3S6 1.00
        D3A1 0.563761
        D3S8 0.906564
        D3A2 3.593680
end
ORCA input line for the second method:
! D4 aug-cc-pVTZ TightSCF DEFGRID3
%method
        method dft
        functional hyb_gga_xc_lc_wpbe08_whs
        D4S6 1.00
        D4A1 0.378
        D4S8 1.170
        D4A2 4.816
end

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&GLOBAL
  PROJECT benchmarking-lcwpbe08-d4
  RUN_TYPE ENERGY
  PRINT_LEVEL LOW
&END GLOBAL

&FORCE_EVAL
        METHOD Quickstep
        &SUBSYS
                &KIND H
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND O
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND C
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND S
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &CELL
                ABC     22.0    22.0    22.0
                PERIODIC NONE
                &END CELL
                &TOPOLOGY
                        &CENTER_COORDINATES T
                        &END CENTER_COORDINATES
                &END TOPOLOGY
                &COORD
    		&END COORD
        &END SUBSYS
        &DFT
                BASIS_SET_FILE_NAME EMSL_BASIS_SETS
                POTENTIAL_FILE_NAME POTENTIAL
                MULTIPLICITY 2
                CHARGE -1
                UKS T
                &QS
                      METHOD GAPW
                      EPS_DEFAULT 1.0E-14
                      EPS_PGF_ORB 1.0E-7
                      EPSFIT 1.0E-8
                &END QS
                &MGRID
                        NGRIDS 4
                        CUTOFF 600
                        REL_CUTOFF 55
                &END MGRID
                &XC
                        &XC_FUNCTIONAL
                          &HYB_GGA_XC_LC_WPBE08_WHS
                           SCALE 1.0
                           _ALPHA 1.00   ! Fraction of HF exchange
                           _BETA -1.00   ! Fraction of short-range exact exchange
                           _OMEGA 0.45   ! Range separation parameter
                          &END
                        &END XC_FUNCTIONAL
                        &HF
                          FRACTION 1.0
                          &SCREENING
                           EPS_SCHWARZ 1.0E-8
                           SCREEN_ON_INITIAL_P FALSE
                          &END SCREENING
                          &INTERACTION_POTENTIAL
                           POTENTIAL_TYPE LONGRANGE
                           OMEGA 0.45
                          &END
                          &MEMORY
                           MAX_MEMORY 3200  ! In MB per MPI rank, use as much to get in-core operation
                           EPS_STORAGE_SCALING 0.1
                          &END MEMORY
                        &END HF
                        &VDW_POTENTIAL
                          DISPERSION_FUNCTIONAL PAIR_POTENTIAL
                          &PAIR_POTENTIAL
                            TYPE DFTD4
                            D4_SCALING 1.000 0.378 1.170 4.816
                          &END PAIR_POTENTIAL
                        &END VDW_POTENTIAL
                &END XC
                &SCF
                        SCF_GUESS ATOMIC
                        EPS_SCF 1.0E-7
                        MAX_SCF 30
                        &OUTER_SCF
                                EPS_SCF 1.0E-7
                                MAX_SCF 10
                        &END OUTER_SCF
                        &OT ON
                                MINIMIZER DIIS
                                PRECONDITIONER FULL_ALL
                        &END OT
                        &MIXING T
                                METHOD BROYDEN_MIXING
                                ALPHA 0.4
                                NBROYDEN 8
                        &END MIXING
                &END SCF
                &POISSON
                        PERIODIC NONE
                        POISSON_SOLVER MT
                &END POISSON
        &END DFT
&END FORCE_EVAL
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&GLOBAL
  PROJECT benchmarking-lcwpbe-d32016
  RUN_TYPE ENERGY
  PRINT_LEVEL LOW
&END GLOBAL

&FORCE_EVAL
        METHOD Quickstep
        &SUBSYS
                &KIND H
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND O
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND C
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &KIND S
                        BASIS_SET aug-cc-pVTZ
                        LEBEDEV_GRID 100
                        RADIAL_GRID 100
                        POTENTIAL ALL
                &END KIND
                &CELL
                ABC     22.0    22.0    22.0
                PERIODIC NONE
                &END CELL
                &TOPOLOGY
                        &CENTER_COORDINATES T
                        &END CENTER_COORDINATES
                &END TOPOLOGY
                &COORD
     		&END COORD
        &END SUBSYS
        &DFT
                BASIS_SET_FILE_NAME EMSL_BASIS_SETS
                POTENTIAL_FILE_NAME POTENTIAL
                MULTIPLICITY 2
                CHARGE -1
                UKS T
                &QS
                      METHOD GAPW
                      EPS_DEFAULT 1.0E-14
                      EPS_PGF_ORB 1.0E-7
                      EPSFIT 1.0E-8
                &END QS
                &MGRID
                        NGRIDS 4
                        CUTOFF 600
                        REL_CUTOFF 55
                &END MGRID
                &XC
                        &XC_FUNCTIONAL
                          &HYB_GGA_XC_LC_WPBE
                           SCALE 1.0
                           _ALPHA 1.00   ! Fraction of HF exchange
                           _BETA -1.00   ! Fraction of short-range exact exchange
                           _OMEGA 0.40   ! Range separation parameter
                          &END
                        &END XC_FUNCTIONAL
                        &HF
                          FRACTION 1.0
                          &SCREENING
                           EPS_SCHWARZ 1.0E-8
                           SCREEN_ON_INITIAL_P FALSE
                          &END SCREENING
                          &INTERACTION_POTENTIAL
                           POTENTIAL_TYPE LONGRANGE
                           OMEGA 0.40
                          &END
                          &MEMORY
                           MAX_MEMORY 3200  ! In MB per MPI rank, use as much to get in-core operation
                           EPS_STORAGE_SCALING 0.1
                          &END MEMORY
                        &END HF
                        &VDW_POTENTIAL
                          DISPERSION_FUNCTIONAL PAIR_POTENTIAL
                          &PAIR_POTENTIAL
                            TYPE DFTD3(BJ)
                            PARAMETER_FILE_NAME dftd3.dat
                            D3BJ_SCALING 1.000000 0.563761 0.906564 3.593680
                          &END PAIR_POTENTIAL
                        &END VDW_POTENTIAL
                &END XC
                &SCF
                        SCF_GUESS ATOMIC
                        EPS_SCF 1.0E-7
                        MAX_SCF 30
                        &OUTER_SCF
                                EPS_SCF 1.0E-7
                                MAX_SCF 10
                        &END OUTER_SCF
                        &OT ON
                                MINIMIZER DIIS
                                PRECONDITIONER FULL_ALL
                        &END OT
                        &MIXING T
                                METHOD BROYDEN_MIXING
                                ALPHA 0.4
                                NBROYDEN 8
                        &END MIXING
                &END SCF
                &POISSON
                        PERIODIC NONE
                        POISSON_SOLVER MT
                &END POISSON
        &END DFT
&END FORCE_EVAL


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