[CP2K-user] [CP2K:14503] Re: TDDFPT calculations with CP2K7.1 using the range-separated functionals

Vladimir Rybkin rybk... at gmail.com
Mon Jan 11 23:07:33 UTC 2021


Sorry, I really read the differences incorrectly. Thank you, Lukas, for 
correcting me. 

понедельник, 11 января 2021 г. в 21:02:30 UTC+1, Lucas Lodeiro: 

> Hi Liu,
> I did not run TDDFT calculations, but I did some tests between CP2K and 
> other programs like G09. As Vladimir says, your basis sets are not the 
> same, and some difference could appear due to this reason. But in your case 
> the differences are big, 1.6 eV approx. I found that some default settings 
> of convergences criterium are differents, for example the *EPS_SCF* which 
> is 1E-8 in G09, you could tight your convergence criterion, *EPS_SCF, *
> *EPS_DEFAULT, **EPS_SCHWARZ* to -8, -12 and -8 to get results with 
> similar convergences in both programs. Also, you are using a PBC 
> calculation in a big cell, but maybe it is no sufficient to mimic the 
> isolated molecule as in G09... and yout cutoff radius for HF is a little 
> bit short, if you run a non-periodic calculation, you can use just the long 
> range potential without the truncation.
> Finally, just to speed up, you can use OT instead of diagonalization 
> method, with it you can use *ADMM_PURIFICATION_METHOD *MO_DIAG.
>
> In order to have the same basis sets, as vladimir says, you could explore  
> to use the same basis sets in both programs, you can get basis sets to both 
> programs from: https://www.basissetexchange.org/
> And the Auxiliary basis set is the minimum one, you could explore FIT and 
> pFIT basis set to check if the result is sensitive.
>
> Regards
> Lucas Lodeiro
>
> El lun, 11 ene 2021 a las 13:01, Vladimir Rybkin (<ry... at gmail.com>) 
> escribió:
>
>> Dear Xiang-Yang Liu,
>>
>> most importantly: you are using different basis sets in Gaussian and CP2K 
>> (CP2K also use pseudopotentials). With this difference in mind you 
>> differences are within reasonable. Generally, difference below 0.1 eV for 
>> TDDFT implementations is not "great".
>>
>> Yours,
>>
>> Vladimir
>>
>> понедельник, 11 января 2021 г. в 14:49:47 UTC+1, lx... at gmail.com: 
>>
>>> Dear All,
>>>
>>> I have tried to use the TDDFPT method implemented in CP2K7.1 to do 
>>> excited state calculations with the range-separated functionals such as 
>>> wB97XD. 
>>> However, after several tests with a small molecule, namely H2Pc, I found 
>>> that the first two excitation energies are greatly underestimated in 
>>> comparison with the LR-TDDFT results obtained in  GAUSSIAN09 (ca. 0.51 and 
>>> 0.60 eV (CP2K7.1) vs. 2.18 and 2.26 eV (GAUSSIAN09)).
>>> I wonder whether there are some mistakes with my input file or there are 
>>> some problem of TDDFPT for such calculations?
>>>
>>> The input file used in my calculations is written as follows:
>>>
>>> *&GLOBAL*
>>> *  PROJECT tddfpt*
>>> *  RUN_TYPE energy*
>>> *  PRINT_LEVEL medium*
>>> *&END GLOBAL*
>>>
>>> *&FORCE_EVAL*
>>> *  METHOD Quickstep*
>>>
>>> *  &PROPERTIES*
>>> *    &TDDFPT*
>>> *       NSTATES  5            # number of excited states*
>>> *    &END TDDFPT*
>>> *  &END PROPERTIES*
>>>
>>> *&DFT*
>>> *    BASIS_SET_FILE_NAME GTH_BASIS_SETS*
>>> *    POTENTIAL_FILE_NAME POTENTIAL*
>>> *    BASIS_SET_FILE_NAME BASIS_ADMM_MOLOPT*
>>> *    BASIS_SET_FILE_NAME BASIS_ADMM*
>>>
>>> *    &AUXILIARY_DENSITY_MATRIX_METHOD*
>>> *      METHOD BASIS_PROJECTION*
>>> *      ADMM_PURIFICATION_METHOD NONE *
>>> *      EXCH_CORRECTION_FUNC BECKE88X*
>>> *    &END AUXILIARY_DENSITY_MATRIX_METHOD*
>>>
>>> *    CHARGE 0 *
>>> *    &MGRID*
>>> *      CUTOFF 400*
>>> *    &END MGRID*
>>> *    &QS*
>>> *      METHOD gpw*
>>> *      EPS_PGF_ORB 1e-12*
>>> *    &END QS*
>>> *    &SCF*
>>> *      MAX_SCF   100*
>>> *      EPS_SCF   1e-5*
>>> *      SCF_GUESS atomic*
>>>
>>> *      &DIAGONALIZATION*
>>> *        ALGORITHM STANDARD*
>>> *      &END DIAGONALIZATION*
>>>
>>> *      &MIXING T*
>>> *        ALPHA 0.5*
>>> *        METHOD PULAY_MIXING*
>>> *        NPULAY 5*
>>> *      &END MIXING*
>>> *    &END SCF*
>>> *    &POISSON*
>>> *       PERIODIC XYZ*
>>> *    &END POISSON*
>>>
>>> *    &XC*
>>> *      &XC_FUNCTIONAL*
>>> *        &LIBXC*
>>> *          FUNCTIONAL HYB_GGA_XC_WB97X_D*
>>> *        &END*
>>> *      &END XC_FUNCTIONAL*
>>> *      &HF*
>>> *       &SCREENING*
>>> *         EPS_SCHWARZ 1.0E-6*
>>> *       &END*
>>> *       &MEMORY*
>>> *         MAX_MEMORY 100*
>>> *       &END*
>>> *       &INTERACTION_POTENTIAL*
>>> *         POTENTIAL_TYPE MIX_CL_TRUNC*
>>> *         OMEGA 0.2*
>>> *         SCALE_LONGRANGE 0.777964*
>>> *         SCALE_COULOMB 0.222036*
>>> *         CUTOFF_RADIUS 5.0*
>>> *         T_C_G_DATA t_c_g.dat*
>>> *       &END*
>>> *      &END*
>>> *      &XC_GRID*
>>> *        XC_DERIV SPLINE2_SMOOTH      # this is needed for the 2nd 
>>> derivatives of the XC functional*
>>> *      &END XC_GRID*
>>> *    &END XC*
>>>
>>> *  &END DFT*
>>> *  &SUBSYS*
>>> *    &TOPOLOGY*
>>> *       &CENTER_COORDINATES*
>>> *       &END CENTER_COORDINATES*
>>> *    &END TOPOLOGY*
>>> *    &CELL*
>>> *      ABC 30.0 30.0 30.0*
>>> *      PERIODIC XYZ*
>>> *    &END CELL*
>>> *    &COORD*
>>> * N                  0.01468800    2.00544200   -0.29683900*
>>> * N                 -2.37562900    2.41155000   -0.13186300*
>>> * N                 -2.41200400   -2.37377100   -0.17491600*
>>> * N                  2.41112400    2.37299900   -0.12658700*
>>> * N                 -0.01307800   -2.00591400   -0.34375500*
>>> * N                  2.37788800   -2.41418900   -0.17065800*
>>> * C                 -4.17222800    0.73645800   -0.00309900*
>>> * C                 -0.67412900    4.18239500    0.01934000*
>>> * C                 -4.18380100   -0.67562700   -0.02014000*
>>> * C                  0.73808000    4.17070300    0.02178600*
>>> * C                 -2.78102300    1.14403300   -0.18692600*
>>> * C                 -1.10192300    2.79691600   -0.16605600*
>>> * C                 -2.79906300   -1.10173400   -0.21220500*
>>> * C                  1.14375300    2.77826000   -0.16260500*
>>> * C                 -0.73890800   -4.16630900   -0.00019300*
>>> * C                  4.18311400    0.67096100    0.00115100*
>>> * C                  0.67355900   -4.17905700    0.00226800*
>>> * C                  4.17314700   -0.74140800   -0.01277100*
>>> * C                 -1.14329800   -2.77792600   -0.20621200*
>>> * C                  2.79688300    1.09912600   -0.17512500*
>>> * C                  1.10326800   -2.79777700   -0.20275300*
>>> * C                  2.78178900   -1.14729500   -0.19912900*
>>> * C                 -5.34524900    1.46617200    0.20504700*
>>> * C                 -1.38645100    5.36877700    0.20954200*
>>> * C                 -5.36863500   -1.39063500    0.17089500*
>>> * C                  1.47037200    5.34443400    0.21437700*
>>> * C                 -6.53049700    0.75063900    0.38667600*
>>> * C                 -0.65342400    6.54324100    0.39406800*
>>> * C                 -6.54209900   -0.66018000    0.36971000*
>>> * C                  0.75719100    6.53149500    0.39645600*
>>> * C                 -1.47251300   -5.33425600    0.22345700*
>>> * C                  5.36943600    1.38205000    0.19903500*
>>> * C                  1.38473700   -5.36039200    0.22884400*
>>> * C                  5.34798200   -1.47459500    0.17084800*
>>> * C                 -0.76071300   -6.51537100    0.44153000*
>>> * C                  6.54461400    0.64821000    0.37381100*
>>> * C                  0.65044900   -6.52827600    0.44412700*
>>> * C                  6.53422100   -0.76263800    0.36007100*
>>> * H                 -5.31982100    2.55648400    0.22741200*
>>> * H                 -2.47726000    5.36199000    0.21499900*
>>> * H                 -5.36047700   -2.48141400    0.16783300*
>>> * H                  2.56090800    5.31878300    0.22274500*
>>> * H                 -7.46690300    1.28881400    0.54987000*
>>> * H                 -1.17840000    7.48942700    0.54335800*
>>> * H                 -7.48727000   -1.18662900    0.52012100*
>>> * H                  1.29740200    7.46875700    0.54746900*
>>> * H                 -2.56294400   -5.30668600    0.23110100*
>>> * H                  5.36158400    2.47267500    0.21857200*
>>> * H                  2.47541900   -5.35281000    0.24119000*
>>> * H                  5.32277600   -2.56515200    0.16738300*
>>> * H                 -1.30192600   -7.44735900    0.61932200*
>>> * H                  7.49034300    1.17231500    0.52877000*
>>> * H                  1.17373400   -7.47001200    0.62407400*
>>> * H                  7.47217800   -1.30348900    0.50426500*
>>> * H                 -0.95410508    0.01210298   -0.52371821*
>>> * H                  0.94993522   -0.00596112   -0.48792422*
>>> * N                 -2.00779500    0.01729500   -0.33767900*
>>> * N                  2.00585900   -0.01636500   -0.31524900*
>>> *    &END COORD*
>>> *    &KIND N*
>>> *      BASIS_SET DZVP-GTH*
>>> *      POTENTIAL GTH-PBE*
>>> *      BASIS_SET AUX_FIT cFIT3*
>>> *    &END KIND*
>>> *    &KIND C*
>>> *      BASIS_SET DZVP-GTH*
>>> *      POTENTIAL GTH-PBE*
>>> *      BASIS_SET AUX_FIT cFIT3*
>>> *    &END KIND*
>>> *    &KIND H*
>>> *      BASIS_SET DZVP-GTH*
>>> *      POTENTIAL GTH-PBE*
>>> *      BASIS_SET AUX_FIT cFIT3*
>>> *    &END KIND*
>>> *  &END SUBSYS*
>>> *&END FORCE_EVAL*
>>>
>>> *Best wishes, *
>>> *Xiang-Yang Liu*
>>>
>> -- 
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>>
>
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