cp2k计算激发态能级和实验测得结果相差较大，请教下如何调整输入文件

ZHUOHAO

各位老师好，我用CP2K算得的S1/T1激发态分析分别为1.058eV/1.057eV，但是实验值为1.80eV/1.76eV。理论计算的结果和实验值差距较大，请教各位老师输入文件部分还有哪些地方可以优化呢？附件上传了以三重态为例的输出文件。谢谢各位老师


#Generated by Multiwfn
&GLOBAL
  PROJECT cp2k-t1-go
  PRINT_LEVEL LOW
  RUN_TYPE GEO_OPT
&END GLOBAL

&FORCE_EVAL
  METHOD Quickstep
  &SUBSYS
    &CELL
      A    35.67300000     0.00000000     0.00000000
      B     0.00000000    30.26500000     0.00000000
      C     0.00000000     0.00000000    36.08200000
      PERIODIC XYZ #Direction(s) of applied PBC (geometry aspect)
    &END CELL
    &COORD
     原子坐标
    &END COORD
    &KIND C
      ELEMENT C
      BASIS_SET DZVP-MOLOPT-SR-GTH-q4
      POTENTIAL GTH-PBE
    &END KIND
    &KIND H
      ELEMENT H
      BASIS_SET DZVP-MOLOPT-SR-GTH-q1
      POTENTIAL GTH-PBE
    &END KIND
    &KIND N
      ELEMENT N
      BASIS_SET DZVP-MOLOPT-SR-GTH-q5
      POTENTIAL GTH-PBE
    &END KIND
    &KIND Zn
      ELEMENT Zn
      BASIS_SET DZVP-MOLOPT-SR-GTH-q12
      POTENTIAL GTH-PBE
    &END KIND
    &KIND Cl
      ELEMENT Cl
      BASIS_SET DZVP-MOLOPT-SR-GTH-q7
      POTENTIAL GTH-PBE
    &END KIND
  &END SUBSYS

  &DFT
    BASIS_SET_FILE_NAME  BASIS_MOLOPT
    POTENTIAL_FILE_NAME  POTENTIAL
#   WFN_RESTART_FILE_NAME cp2k-t1-go-RESTART.wfn
    CHARGE    0 #Net charge
    MULTIPLICITY    1 #Spin multiplicity
    &QS
      EPS_DEFAULT 1.0E-12 #Set all EPS_xxx to values such that the energy will be correct up to this value
    &END QS
    &POISSON
      PERIODIC XYZ #Direction(s) of PBC for calculating electrostatics
      PSOLVER PERIODIC #The way to solve Poisson equation
    &END POISSON
    &XC
      &XC_FUNCTIONAL PBE
      &END XC_FUNCTIONAL
          &VDW_POTENTIAL
        POTENTIAL_TYPE PAIR_POTENTIAL
        &PAIR_POTENTIAL
          PARAMETER_FILE_NAME dftd3.dat
          TYPE DFTD3(BJ)
          REFERENCE_FUNCTIONAL PBE
          #CALCULATE_C9_TERM T #Calculate C9-related three-body term, more accurate for large system
        &END PAIR_POTENTIAL
      &END VDW_POTENTIAL
    &END XC
    &MGRID
      CUTOFF  350
      REL_CUTOFF  50
    &END MGRID
    &SCF
      MAX_SCF 128
      EPS_SCF 1.0E-06 #Convergence threshold of density matrix of inner SCF
#     SCF_GUESS RESTART #Use wavefunction from WFN_RESTART_FILE_NAME file as initial guess
      &DIAGONALIZATION
        ALGORITHM STANDARD #Algorithm for diagonalization
      &END DIAGONALIZATION
      &MIXING #How to mix old and new density matrices
        METHOD BROYDEN_MIXING #PULAY_MIXING is also a good alternative
        ALPHA 0.4 #Default. Mixing 40% of new density matrix with the old one
        NBROYDEN 8 #Default is 4. Number of previous steps stored for the actual mixing scheme
      &END MIXING
      ADDED_MOS    30 #Number of virtual MOs to solve
      &PRINT
        &RESTART #Note: Use "&RESTART OFF" can prevent generating .wfn file
          BACKUP_COPIES 0 #Maximum number of backup copies of wfn file. 0 means never
        &END RESTART
      &END PRINT
    &END SCF
    &PRINT
      &MO_MOLDEN #Exporting .molden file containing wavefunction information
        NDIGITS 9 #Output orbital coefficients if absolute value is larger than 1E-9
      &END MO_MOLDEN
    &END PRINT
  &END DFT
  &PROPERTIES
    &TDDFPT #TDDFT calculation with Tamm-Dancoff approximation
      NSTATES   5 #Number of excited states to solve
      RKS_TRIPLETS T #If calculating triplet rather than singlet excited states
      CONVERGENCE [eV] 1E-4 #Convergence criterion of all excitation energies
      MIN_AMPLITUDE 0.01 #The smallest excitation amplitude to print
#     RESTART T #If restarting TDDFT calculation. If true, WFN_RESTART_FILE_NAME should be set to previous .tdwfn file
#     WFN_RESTART_FILE_NAME cp2k-t1-go-RESTART.tdwfn
      &PRINT
        #&DETAILED_ENERGY #Print excitation energies at every Davidson iteration
        #&END DETAILED_ENERGY
      &END PRINT
    &END TDDFPT
  &END PROPERTIES
&END FORCE_EVAL

&MOTION
  &GEO_OPT
    TYPE MINIMIZATION #Search for minimum
    KEEP_SPACE_GROUP F #If T, then space group will be detected and preserved
    OPTIMIZER BFGS #Can also be CG (more robust for difficult cases) or LBFGS
    &BFGS
      TRUST_RADIUS 0.2 #Trust radius (maximum stepsize) in Angstrom
#     RESTART_HESSIAN T #If read initial Hessian, uncomment this line and specify the file in the next line
#     RESTART_FILE_NAME to_be_specified
    &END BFGS
    MAX_ITER 500 #Maximum number of geometry optimization
    MAX_DR 3E-3 #Maximum geometry change
    RMS_DR 1.5E-3 #RMS geometry change
    MAX_FORCE 4.5E-4 #Maximum force
    RMS_FORCE 3E-4 #RMS force
  &END GEO_OPT
  &PRINT
    &TRAJECTORY
      FORMAT xyz
    &END TRAJECTORY
    &RESTART
      BACKUP_COPIES 0 #Maximum number of backing up restart file, 0 means never
    &END RESTART
  &END PRINT
&END MOTION

yjb

初始结构优化了吗？

sobereva

用纯泛函必定低估激发能
看此文了解常识
乱谈激发态的计算方法
http://sobereva.com/265（http://bbs.keinsci.com/thread-415-1-1.html）

ZHUOHAO

yjb 发表于 2023-12-2 21:39
初始结构优化了吗？

初始结构已经优化过了

ZHUOHAO

sobereva 发表于 2023-12-3 00:24
用纯泛函必定低估激发能
看此文了解常识
乱谈激发态的计算方法

好的，谢谢老师。我再去学习一下