[CP2K-user] [CP2K:14503] Re: TDDFPT calculations with CP2K7.1 using the range-separated functionals
liu xiangyang
lxyl... at gmail.com
Tue Jan 12 04:49:24 UTC 2021
Hi Vladimir & Lucas，
Thanks a lot for your kindly responses. Actually, I have also tested small
molecule such as H2CO using present settings and the results obtained by
CP2K and G09 are quanlitatively in good agreement with each other and THAT
IS THE FACT THAT PUZZLES ME MOST.
According to your suggestions, I have made several changes to my input
file, including removal of the periodic conditions, removal of the ADMM
approximations to avoid possible mistakes, and lower the convergence in
G09 since the computational efforts of CP2K is much larger. The basis sets
are not changed since the TDDFPT in CP2K is implemented only in GPW method,
which is unable to do calculations with all electron basis sets such as
Pople basis sets. However, I believe the difference of basis set (DZVP-GTH
vs. 6-31G*) should not be so large. Unfortunately, the results of CP2K7.1
is still about 1 eV lower than that obtained in G09 (1.19 and 1.25 eV in
CP2K vs. 2.18 and 2.26 eV in G09).
PS. I have also run GAPW calculations in CP2K using the WB97XD/6-31G** and
the resulted ground state energy are nearly the same as that obtained in
G09 (differenceless than 0.002 hartree).
The modified DFT parts of CP2K input file is attatched also:
&DFT
BASIS_SET_FILE_NAME BASIS_MOLOPT
POTENTIAL_FILE_NAME POTENTIAL
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 NONE
PSOLVER MT
&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
OMEGA 0.2
SCALE_LONGRANGE 0.777964
SCALE_COULOMB 0.222036
&END
&END
&END XC
&END DFT
Best wishes,
Xiang-Yang Liu
On Tuesday, January 12, 2021 at 7:07:34 AM UTC+8 ry... at gmail.com wrote:
> 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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