[QE-users] [QE users] pseudopotential hardness and transferability

Aldo Ugolotti a.ugolotti at campus.unimib.it
Thu Apr 2 18:16:46 CEST 2020


Dear Nicola,

thanks for your reply. I mentioned the energy criteria for convergence 
as the simplest one to verify.

Regarding the pseudos you mentioned (PBE), those available at the 
materialscloud portal, I have checked them either in the atomic case and 
for a simple system of interest. In the latter case, I found that the 
required minimal cutoffs are ~90/225 Ry while in the former case the 
results of ld1.x (for Hamiltonian evaluation with Bessel functions) are 
consistent with the numbers you reported.

For both N and C pseudos the test on electronic configurations with more 
electrons fail as the scf cycle does not converge, both for AE and PS 
wavefucntions.

If I understood correctly the works you referred to, the delta parameter 
seems much more large-scale (i.e. code to code) than the scope I am 
working in, as I am not validating a pseudo generation procedure, (which 
I am assuming to be already accurate, given the source) but rather I am 
trying to understand the system-dependency of the behavior of the 
pseudo. However, I am mistaken, I will be glad to check those papers 
again and run some tests.

Bests Regards,

-- 
Aldo Ugolotti, Ph.D.

Post-doc fellow
Materials Science Dept. U5,
Università degli Studi di Milano-Bicocca
via Cozzi 55,
20125 Milano (MI)
Italy
e-mail: a.ugolotti at campus.unimib.it


On 02/04/20 13:39, Nicola Marzari wrote:
>
>
>
> Dear Aldo,
>
>
> very worthwhile work! Also very hard (pun intended) - pseudopotential 
> generation is not an easy task. In particular, you can make things 
> softer, but less accurate, and that's not one wants. Also, being at a 
> cutoff that converges the total energy is not superinteresting - we 
> typically want stresses, forces, et al to be both converged (easy to 
> test), and accurate (more difficult, you need to compare with 
> all-electron calculations, ideally in some real-life solid state 
> systems).
>
> If you go to https://www.materialscloud.org/discover/sssp/ you could 
> acquaint yourself with a couple of papers on verification (see section
> "How to cite") and on pseudopotential generation (see section 
> "Acknolwedgments").
>
> You could also try out the C and N pseudopotentials from the PBE or
> PBEsol SSSP efficiency library, and see if you really need to have 
> larger cutoffs than those suggested (45/360 Ry for ecutwfc and ecutrho 
> respectively (i.e. a dual of 8) for the carbon pseudopotential, taken 
> as PAW from pslibrary 1.0, and 60/480 Ry for N, generated by me). The 
> delta value for the elemental solid is a first measure of how good 
> things are with respect to all electron results.
>
>                 nicola
>
>
>
>
>
> On 02/04/2020 13:15, Aldo Ugolotti wrote:
>> Dear QE users,
>>
>> I am actually working on a system with C and N atoms. Checking the 
>> convergence of the total energy for finding the optimal values for 
>> the cutoffs (i.e. DE ~ 1mRy), I found that, despite in the atomic 
>> case the suggested values (for example the wfc cutoff are ~ 46 Ry for 
>> both) are good enough, in a sample of my system which is already 
>> relaxed (and whose geometry is in good agreement with reported 
>> results) the same convergence check determines a cutoff which is, 
>> again for example for the wavefunction, 2 to 3 times larger.
>>
>> As I tried to modify the pseudo to make it softer, I have also run 
>> some transferability tests, which I am curious to hear your opinion 
>> about. In particular, the tests were running fine for the testing 
>> configurations with less electrons (e.g. 2s2 2p1 for C) but there 
>> were problems with tests with more electrons (e.g. 2s2 2p3 for C). In 
>> those cases the scf cycles did not converge at all, both at AE or PS 
>> level.
>>
>> I found the same result with the pseudo US,PAW in the pslibrary of 
>> different versions, namely 1.0.0, 0.3.1 and 0.1. I also tried to 
>> change the radii, the local potential (adding a 3D empty orbital), 
>> the configuration (e.g, Ztot=5.5, Zval 1.5 for C) or the pseudization 
>> recipe (TM/RRKJUS).
>>
>> Hence, I got few questions:
>>
>> i) is it really a transferability issue, or do I need "only" to get 
>> those scf cycles to converge? how?
>>
>> ii) if the pseudo is not good to represent electronic configurations 
>> with more electrons, that would be a viable explanation as to why the 
>> cutoffs for a sample systems are so much larger than the atomic cases?
>>
>> Below I am reporting the output for the test of the configtf(2)='2s2 
>> 2p3'
>>
>>
>>       Message from routine scf:
>>       warning: convergence not achieved
>>       --------------------------- All-electron run 
>> ----------------------------
>>
>> C
>>       scalar relativistic calculation
>>
>>       atomic number is  6.00
>>       dft =SLA PW PBX PBC   lsd =0 sic =0 latt =0  beta=0.20 tr2=1.0E-14
>>       Exchange-correlation      = SLA PW PBX PBC ( 1  4  3  4 0 0)
>>       mesh =1073 r(mesh) = 100.30751 a.u. xmin = -7.00 dx = 0.01250
>>       1 Ry =  13.60569193 eV, c = 137.03599966
>>
>>       n l     nl                  e(Ry)          e(Ha) e(eV)
>>       1 0     1S 1( 2.00)       -19.6664        -9.8332 -267.5745
>>       2 0     2S 1( 2.00)        -0.6297        -0.3148 -8.5669
>>       2 1     2P 1( 3.00)        -0.0290        -0.0145 -0.3951
>>
>>       final scf error:  2.4E-01 reached in 201 iterations
>>
>>       Etot =     -78.638531 Ry,     -39.319266 Ha, -1069.931632 eV
>>
>>       Ekin =      73.218424 Ry,      36.609212 Ha, 996.187324 eV
>>       Encl =    -182.081805 Ry,     -91.040902 Ha, -2477.348944 eV
>>       Eh   =      40.989732 Ry,      20.494866 Ha, 557.693668 eV
>>       Exc  =     -10.764883 Ry,      -5.382441 Ha, -146.463680 eV
>>
>>
>>       normalization and overlap integrals
>>
>>       s(1S/1S) =  1.000000  <r> =   0.2707  <r2> = 0.0993  r(max) =   
>> 0.1730
>>       s(1S/2S) = -0.000112
>>       s(2S/2S) =  1.000000  <r> =   1.6236  <r2> = 3.2283  r(max) =   
>> 1.2315
>>       s(2P/2P) =  1.000000  <r> =   2.1244  <r2> = 6.4268  r(max) =   
>> 1.2470
>>
>>       ------------------------ End of All-electron run 
>> ------------------------
>>
>>       Message from routine run_pseudo:
>>       Warning: convergence not achieved
>>
>>       ---------------------- Testing the pseudopotential 
>> ----------------------
>>
>> C
>>       scalar relativistic calculation
>>
>>       atomic number is  6.00   valence charge is  4.00
>>       dft =SLA PW PBX PBC   lsd =0 sic =0 latt =0  beta=0.20 tr2=1.0E-14
>>       mesh =1073 r(mesh) = 100.30751 xmin = -7.00 dx = 0.01250
>>
>>       n l     nl             e AE (Ry)        e PS (Ry)    De AE-PS (Ry)
>>       1 0     2S   1( 2.00)       -0.62966       -0.17919 -0.45046  !
>>       2 1     2P   1( 3.00)       -0.02904       -0.00000 -0.02904  !
>>
>>       eps = 3.2E-04  iter =201
>>
>>       Etot =     -78.638531 Ry,     -39.319266 Ha, -1069.931632 eV
>>       Etotps =   -18.974270 Ry,      -9.487135 Ha, -258.158068 eV
>>       dEtot_ae =      -3.108582 Ry
>>       dEtot_ps =      -1.208418 Ry,   Delta E=      -1.900164 Ry
>>
>>       Ekin =      10.222924 Ry,       5.111462 Ha, 139.089950 eV
>>       Encl =     -31.022876 Ry,     -15.511438 Ha, -422.087699 eV
>>       Ehrt =      12.620743 Ry,       6.310371 Ha, 171.713935 eV
>>       Ecxc =     -10.795060 Ry,      -5.397530 Ha, -146.874254 eV
>>       (Ecc =      -0.958640 Ry,      -0.479320 Ha, -13.042955 eV)
>>
>>       ---------------------- End of pseudopotential test 
>> ----------------------
>>
>>
>>       -------------- Test with a basis set of Bessel functions 
>> ----------
>>
>>       Box size (a.u.) :   30.0
>>
>>       Cutoff (Ry) :   30.0
>>                             N = 1       N = 2       N = 3
>>       E(L=0) =        -0.1788 Ry    0.1213 Ry    0.1854 Ry
>>       E(L=1) =         0.1263 Ry    0.1949 Ry    0.2715 Ry
>>
>>       Cutoff (Ry) :   60.0
>>                             N = 1       N = 2       N = 3
>>       E(L=0) =        -0.1789 Ry    0.1213 Ry    0.1854 Ry
>>       E(L=1) =         0.1263 Ry    0.1949 Ry    0.2715 Ry
>>
>>       Cutoff (Ry) :   90.0
>>                             N = 1       N = 2       N = 3
>>       E(L=0) =        -0.1789 Ry    0.1213 Ry    0.1854 Ry
>>       E(L=1) =         0.1263 Ry    0.1949 Ry    0.2715 Ry
>>
>>       Cutoff (Ry) :  120.0
>>                             N = 1       N = 2       N = 3
>>       E(L=0) =        -0.1789 Ry    0.1213 Ry    0.1854 Ry
>>       E(L=1) =         0.1263 Ry    0.1948 Ry    0.2715 Ry
>>
>>       -------------- End of Bessel function test 
>> ------------------------
>>
>>
>> Thank you in advance,
>>
>
>
-- 
Aldo Ugolotti, Ph.D.

Post-doc fellow
Materials Science Dept. U5,
Università degli Studi di Milano-Bicocca
via Cozzi 55,
20125 Milano (MI)
Italy
e-mail: a.ugolotti at campus.unimib.it



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