[CP2K-user] [CP2K:20184] Charged system with tddft, problem in energies

Jürg Hutter hutter at chem.uzh.ch
Mon May 6 15:12:40 UTC 2024


Hi
there most be something wrong with your ground state SCF.
Try to get it properly converged first. No negative HOME-LUMO gap!
regards
JH

________________________________________
From: cp2k at googlegroups.com <cp2k at googlegroups.com> on behalf of Nóra Kovács <nonoka4418 at gmail.com>
Sent: Monday, May 6, 2024 3:15 PM
To: cp2k
Subject: [CP2K:20182] Charged system with tddft, problem in energies

Hi all!
I have a problem with charged systems. I read that there should be automatically a charge background correction in cp2k. I wanted to put -1 charge on my periodic solid system and it gives me unrealistic HOMO-LUMO gap as well as excitation energies.
My uncharged system has a band gap of ca. 4eV
with the extra charge it is -4ev and also the excitation energies are:
TDDFPT|      1      -4.90388   6.6514E-02  1.1237E-01  6.9805E-02  -2.63401E-03
 TDDFPT|      2      -4.41576   1.5198E-02  7.6006E-02  4.8727E-02  -9.06818E-04
 TDDFPT|      3      -3.06657   3.1150E-01  2.4287E-01  1.6674E-01  -1.38103E-02
 TDDFPT|      4      -0.86657   1.0274E+00  5.7287E-01  6.6111E-01  -3.86559E-02
 TDDFPT|      5      -0.73913   2.1315E+00  1.9346E+00  3.7857E-01  -1.52639E-01
 TDDFPT|      6      -0.70470   4.0579E+00  1.7798E+00  8.2125E-01  -3.50632E-01
 TDDFPT|      7      -0.67319   7.4310E+00  3.8930E+00  3.2962E-01  -1.16248E+00
 TDDFPT|      8      -0.63574   1.4686E+00  1.1029E+00  2.5738E-01  -5.35724E-02
 TDDFPT|      9      -0.62635   7.3774E+00  3.9100E+00  6.9441E-01  -1.07719E+00
 TDDFPT|     10      -0.60103   6.9763E+00  2.9443E+00  7.6770E-01  -8.52972E-01

Can someone tell me why this is happening or is there some problem in my input file (see down).
Thank you!!!!
Nora Kovacs

input:
&GLOBAL
  PROJECT opt32_charged
  RUN_TYPE ENERGY
  PREFERRED_DIAG_LIBRARY SL
  PRINT_LEVEL medium
&END GLOBAL


&FORCE_EVAL
  METHOD Quickstep


&PROPERTIES

      &TDDFPT                          ! input section for TDDFPT
       KERNEL FULL                       ! specification of the underlying kernel matrix K
                                         ! FULL kernel is for GGA and hybrid functional computations
                                         ! sTDA kernel is referring to a semi-empirical sTDA computation
       NSTATES 10                      ! specifies the number of excited states to be computed
       MAX_ITER   100                  ! number of iterations for the Davidson algorithm
       CONVERGENCE [eV] 1.0e-5         ! convergence threshold in eV
       NLUMO 400
       RKS_TRIPLETS F                  ! Keyword to choose between singlet and triplet excitations
       &MGRID
          CUTOFF 550  # separate cutoff for TDDFPT calc
       &END

       &PRINT
         &NTO_ANALYSIS
           CUBE_FILES
         &END NTO_ANALYSIS
       &END PRINT
    &END TDDFPT
  &END PROPERTIES


&DFT
    BASIS_SET_FILE_NAME BASIS_MOLOPT
    BASIS_SET_FILE_NAME BASIS_ADMM
    BASIS_SET_FILE_NAME BASIS_ADMM_MOLOPT
    POTENTIAL_FILE_NAME POTENTIAL
    LSD
    !WFN_RESTART_FILE_NAME opt32_charged-RESTART.wfn
    SURFACE_DIPOLE_CORRECTION .TRUE.
    CHARGE -1
    &MGRID
      CUTOFF 250
    &END MGRID

    &QS
      METHOD GPW
      EPS_DEFAULT 1.0E-17
      EPS_PGF_ORB 1.0E-30
    &END QS

    &POISSON
       PERIODIC XYZ #Direction(s) of PBC for calculating electrostatics
       PSOLVER PERIODIC #The way to solve Poisson equation
    &END POISSON

    &AUXILIARY_DENSITY_MATRIX_METHOD
            METHOD BASIS_PROJECTION
            ADMM_PURIFICATION_METHOD NONE
            EXCH_CORRECTION_FUNC PBEX
    &END AUXILIARY_DENSITY_MATRIX_METHOD

    &SCF
      SCF_GUESS RESTART #Use wavefunction from WFN_RESTART_FILE_NAME file as initial guess
      MAX_SCF   700
      EPS_SCF   5.0E-4
!      ADDED_MOS 100
      CHOLESKY INVERSE
      &OT .TRUE.
      &END OT

      &MIXING
          METHOD BROYDEN_MIXING
          ALPHA 0.2
          BETA 0.2 #1.5
          NBROYDEN 8
      &END
    &END SCF

    &PRINT
       &MO_CUBES
           WRITE_CUBE F
           NHOMO 1
           NLUMO 1
       &END MO_CUBES
       &PDOS
        NLUMO -1
        COMPONENTS T
        !LIST
       &END
    &END PRINT


    &XC
      &XC_FUNCTIONAL

       &PBE
          SCALE_X 0.75
          SCALE_C 1.0
        &END PBE
      &END XC_FUNCTIONAL
      &XC_GRID
         XC_DERIV SPLINE3_SMOOTH
      &END XC_GRID
      &HF
        &SCREENING
          EPS_SCHWARZ 1.0E-6
          SCREEN_ON_INITIAL_P .TRUE.
        &END SCREENING
        &INTERACTION_POTENTIAL
          POTENTIAL_TYPE TRUNCATED
          CUTOFF_RADIUS 8.0
          T_C_G_DATA ./t_c_g.dat
        &END
        &MEMORY
          MAX_MEMORY 4000
          EPS_STORAGE_SCALING 0.1
        &END
         FRACTION 0.25
      &END HF
    &END XC
  &END DFT

  &SUBSYS
    &KIND W
            POTENTIAL GTH-PBE
            POTENTIAL_TYPE GTH
            BASIS_SET DZVP-MOLOPT-SR-GTH
            BASIS_SET AUX_FIT cFIT10
    &END KIND
    &KIND Nb
            POTENTIAL GTH-PBE
            BASIS_SET DZVP-MOLOPT-SR-GTH
            POTENTIAL_TYPE GTH
            BASIS_SET AUX_FIT cFIT10
    &END KIND
    &KIND O
            POTENTIAL GTH-PBE
            BASIS_SET DZVP-MOLOPT-SR-GTH
            POTENTIAL_TYPE GTH
            BASIS_SET AUX_FIT cFIT3
    &END KIND

    &KIND Li
            POTENTIAL GTH-PBE
            BASIS_SET DZVP-MOLOPT-SR-GTH
            POTENTIAL_TYPE GTH
            BASIS_SET AUX_FIT cFIT3
    &END KIND

    &CELL
      A     18.79885064 0.0000000000000000 0.0000000000000000
      B     0.0000000000000000  18.79885064 0.0000000000000000
      C     0.0000000000000000 0.0000000000000000 62.63355178
      PERIODIC XYZ
    &END CELL
    &TOPOLOGY
        COORD_FILE_NAME     opt32.xyz
        COORD_FILE_FORMAT   XYZ
    &END TOPOLOGY
  &END SUBSYS
&END FORCE_EVAL

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