[Pw_forum] Mo pseudopotential
Andrea Dal Corso
dalcorso at sissa.it
Fri Mar 29 16:38:49 CET 2013
On Tue, 2013-03-26 at 17:54 -0700, mgtmentink at lbl.gov wrote:
>
>
> ----- Reply message -----
> From: "Ary Junior" <aryjunior at gmail.com>
> To: "PWSCF Forum" <pw_forum at pwscf.org>
> Subject: [Pw_forum] Mo pseudopotential
> Date: Tue, Mar 26, 2013 2:38 pm
>
>
>
> Dear all,
>
> I was looking for a PBE USPP for molybdenum and checked that the .UPF
> files available in the QE website are the ones provided in pslibrary
> 0.2... So, based in the input file I created a test for the
> Mo.pbe-spn-rrkjus_psl.0.2.UPF file like this:
>
> &input
> title='Mo',
> zed=42.0,
> rel=1,
> config='[Kr] 4d5.0 5s1 5p0',
> iswitch=2,
> dft='PBE',
> rlderiv=2.93, eminld=-3.0, emaxld=3.0, deld=0.01, nld=3
> /
> &test
> file_pseudo='Mo.pbe-spn-rrkjus_psl.0.2.UPF',
> nconf=1,
> configts(1)='4d5.0 5s1 5p0',
> ecutmin=50, ecutmax=200, decut=50
> /
>
The Mo of the pslibrary has 4s and 4p semicore states in the valence, so
you have to include them in the test configuration. With something like:
configts(1)='4s2.0 4p6.0 4d5.0 5s1 5p0'
the pp seems to work.
HTH,
Andrea
> Besides some warnings after the "All-electron run" section, the
> difference between the AE and the PS eigenvalues are zero and it is
> ok...
>
> n l nl e AE (Ry) e PS (Ry) De AE-PS
> (Ry)
> 3 2 4D 1( 5.00) -0.27582 -0.27582
> 0.00000
> 1 0 5S 1( 1.00) -0.30033 -0.30033
> 0.00000
> 2 1 5P 1( 0.00) -0.07669 -0.07669
> 0.00000
>
> However, when compare these eigenvalues with an atomic calculation
> using the spherical Bessel functions I got a weird result, even with a
> high cutoff energy:
>
> Cutoff (Ry) : 200.0
> N = 1 N = 2 N = 3
> E(L=0) = -23.1157 Ry -13.3019 Ry -9.0812 Ry
> E(L=1) = -20.7569 Ry -11.9179 Ry -7.7609 Ry
> E(L=2) = -17.0812 Ry -9.9089 Ry -6.4930 Ry
>
> Moreover, the AE vs PS logarithmic derivatives are quite discrepant,
> even at lower r values... The point is that after analyzing the shape
> of the AE orbitals I couldn't understand the so low rcut values in the
> pslibrary input file in both versions, 0.2 and 0.3... I have done the
> same test for other PBE USPPs available in the QE website like
> Ni.pbe-n-rrkjus_psl.0.1.UPF, O.pbe-n-rrkjus_psl.0.1.UPF and
> S.pbe-n-rrkjus_psl.0.1.UPF and they are fine... So, I tried to reset
> the input file with radii more compatible with the AE wavefunctions in
> my conception, besides change the core corrections like this:
>
> &input
> title='Mo',
> prefix='Mo',
> zed=42.0,
> config='[Kr] 5s1 4d5 5p0',
> iswitch=3,
> dft='PBE',
> rlderiv=2.93, eminld=-3.0, emaxld=3.0, deld=0.01, nld=3,
> /
> &inputp
> pseudotype=3,
> file_pseudopw='Mo.PBE-spn-rrkjus_aryjr.UPF',
> author='ADC',
> lloc=-1,
> rcloc=3.2,
> which_augfun='PSQ',
> rmatch_augfun=1.3,
> nlcc=.true.,
> new_core_ps=.true.,
> rcore=1.0,
> tm=.true.
> /
> 6
> 5S 1 0 1.00 0.00 2.70 3.30 0.0
> 5S 1 0 0.00 7.00 2.50 3.30 0.0
> 5P 2 1 0.00 0.00 3.20 3.30 0.0
> 5P 2 1 0.00 7.00 3.20 3.30 0.0
> 4D 3 2 5.00 0.00 1.50 1.70 0.0
> 4D 3 2 0.00 -0.30 0.70 1.70 0.0
>
> Then, I think that everything is fine with the AE and the PS
> eigenvalues:
>
> n l nl e AE (Ry) e PS (Ry) De AE-PS
> (Ry)
> 1 0 5S 1( 1.00) -0.30033 -0.30033
> 0.00000
> 3 2 4D 1( 5.00) -0.27582 -0.27582
> 0.00000
> 2 1 5P 1( 0.00) -0.07669 -0.07669
> -0.00000
>
> And after compare these eigenvalues with an atomic calculation using
> the spherical Bessel functions again, things look better now:
>
> Cutoff (Ry) : 50.0
> N = 1 N = 2 N = 3
> E(L=0) = -0.3002 Ry -0.0021 Ry 0.0380 Ry
> E(L=1) = -0.0766 Ry 0.0213 Ry 0.0681 Ry
> E(L=2) = -0.2681 Ry 0.0313 Ry 0.0692 Ry
>
> Cutoff (Ry) : 200.0
> N = 1 N = 2 N = 3
> E(L=0) = -0.3002 Ry -0.0021 Ry 0.0380 Ry
> E(L=1) = -0.0766 Ry 0.0213 Ry 0.0681 Ry
> E(L=2) = -0.2683 Ry 0.0313 Ry 0.0692 Ry
>
> The AE vs PS logarithmic derivatives are being well reproduced in
> energies lower than 1 Ry.... I also tested chemical states like the
> ionized Mo4+ and Mo6+, and the results are listed below:
>
> 1 0 5S 1( 1.00) -0.30033 -0.30033
> 0.00000
> 3 2 4D 1( 5.00) -0.27582 -0.27582
> 0.00000
> 2 1 5P 1( 0.00) -0.07669 -0.07669
> -0.00000
> Etot = -8097.243530 Ry, -4048.621765 Ha, -110168.600949 eV
> Etotps = -32.753518 Ry, -16.376759 Ha, -445.634282 eV
>
> 1 0 5S 1( 0.00) -2.69065 -2.78173
> 0.09108
> 3 2 4D 1( 2.00) -3.40343 -3.51010
> 0.10667
> 2 1 5P 1( 0.00) -2.17762 -2.27343
> 0.09581
> dEtot_ae = 6.511981 Ry
> dEtot_ps = 6.625031 Ry, Delta E= -0.113050 Ry
>
> 1 0 5S 1( 0.00) -4.30796 -4.58873
> 0.28077
> 3 2 4D 1( 0.00) -5.60739 -5.87530
> 0.26791
> 2 1 5P 1( 0.00) -3.66423 -3.99180
> 0.32756
> dEtot_ae = 15.474602 Ry
> dEtot_ps = 15.954369 Ry, Delta E= -0.479767 Ry
>
> My question: is my procedure described above wrong? Study and
> understand the generation of PSPs is not easy for me and I'm trying to
> learn it grounded in some textbooks as well as some documents spread
> on the internet and of course the input files provided in the
> pslibrary project. But this PBE USPP for molybdenum made me a little
> bit confused. I tested both in a MoS2 unit cell with PBE-D and the
> cell volume as well as the interatomic distances are fine if compared
> with the experiments, with differences lower than 3%... One more
> question: how can I improve the result for the Mo4+ and Mo6+ ionized
> states?
>
> Thank you very much!
>
> Ary Junior
>
> Doctoral Student
> Chemistry Department
> Universidade Federal de Juiz de Fora - MG - Brasil
>
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Andrea Dal Corso Tel. 0039-040-3787428
SISSA, Via Bonomea 265 Fax. 0039-040-3787249
I-34136 Trieste (Italy) e-mail: dalcorso at sissa.it
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