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 > > -- > http://lattes.cnpq.br/8221674673413336 > _______________________________________________ > Pw_forum mailing list > Pw_forum at pwscf.org > http://pwscf.org/mailman/listinfo/pw_forum -- 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
