[QE-users] Phonon: negative frequencies for adsorbate molecule using "nat-todo" option

Tamas Karpati tkarpati at gmail.com
Wed Nov 4 19:48:27 CET 2020


In addition to my earlier comments, i'd like to mention that for kinetics
you most probably need an SO2 simulation (optimization+phonons)
rather than the same for a surface attached SO2 or SO+O. Big difference!

Back to the earliers, 3-atoms phonon is so unphysical that it is
recommended to do an all-atom one, or add at least the directly
bonded surface atoms (and extend towards all-atoms if you can).

In addition, only all-atom phonon will show you whether your big negative
freqs. indicate a non-minimum structure (ie. "freqs" ~ 2nd derivatives
of the PEHS).
With somewhat less atoms you can be lucky, and by visualizing normal
modes (phonons) by eg. XCrysDen will show you where to move atoms
to get into the local minimum. Kinetics theory builds on minima (and TS-es).
Anyways, 3 atoms are too few (also see first section above).

On Mon, Nov 2, 2020 at 11:29 AM Tamas Karpati <tkarpati at gmail.com> wrote:
>
> Dear Omer,
>
> I guess that your input is fine, your structure is not.
> (By the way, tr2_ph could be lower.)
>
> You woud expect 6 near zero and 3N-6 positive freqs. for a completely
> relaxed minimum structure (and 5 + 3N-5 for a TS).
> This is ruined if you run PH.x on a different potential energy
> hypersurface, PEHS.
>
> It is really very easy to spoil: use a different no. of k point or functional
> for PW/vc-relax and PH and you're there. Another temptation is to
> use experimental crystal structure and fix some/most atoms as such.
> These all mean different PEHS'.
> In addition, unconverged relaxation (or too loose convergence),
> while moves on the same PEHS, provides you with inappropriate
> freqs, as it does not bring your structure close enough to the local minimum.
>
> I would recommend to reconsider the "life" of your structure
> (origin, optimization method, other parameters) and adjust if necessary.
>    t
>
> On Mon, Nov 2, 2020 at 7:43 AM Omer Mutasim <omermutasim at ymail.com> wrote:
> >
> >  Dear all
> >
> >  I'm doing phonon calculation at Gamma point (q)  in order to estimate the reaction rate constants for a micro-kinetic model.  I have perturbed only the adsorbate molecule with the 3 surface atoms, connected to adsorbate, using "nat-todo" option. However, i got 15 negative frequencies (should be 6 as i know ) ,with high absolute value.
> >
> > Can you please help me to know what is wrong with my input files ?
> >
> > Below are the output & input files:
> >
> >
> >
> >      Mode symmetry, C_1 (1)     point group:
> >
> >      freq (  1 -  1) =      -2762.6  [cm-1]   --> A               I+R
> >      freq (  2 -  2) =      -2570.3  [cm-1]   --> A               I+R
> >      freq (  3 -  3) =      -2460.4  [cm-1]   --> A               I+R
> >      freq (  4 -  4) =      -2423.6  [cm-1]   --> A               I+R
> >      freq (  5 -  5) =      -2356.3  [cm-1]   --> A               I+R
> >      freq (  6 -  6) =      -2158.0  [cm-1]   --> A               I+R
> >      freq (  7 -  7) =      -2151.1  [cm-1]   --> A               I+R
> >      freq (  8 -  8) =      -2067.5  [cm-1]   --> A               I+R
> >      freq (  9 -  9) =      -2034.8  [cm-1]   --> A               I+R
> >      freq ( 10 - 10) =      -2025.2  [cm-1]   --> A               I+R
> >      freq ( 11 - 11) =      -1864.3  [cm-1]   --> A               I+R
> >      freq ( 12 - 12) =      -1804.5  [cm-1]   --> A               I+R
> >      freq ( 13 - 13) =      -1099.4  [cm-1]   --> A               I+R
> >      freq ( 14 - 14) =       -947.6  [cm-1]   --> A               I+R
> >      freq ( 15 - 15) =       -912.5  [cm-1]   --> A               I+R
> >      freq (316 -316) =        179.3  [cm-1]   --> A               I+R
> >      freq (317 -317) =        193.0  [cm-1]   --> A               I+R
> >      freq (318 -318) =        215.8  [cm-1]   --> A               I+R
> >      freq (319 -319) =        240.2  [cm-1]   --> A               I+R
> >      freq (320 -320) =        270.4  [cm-1]   --> A               I+R
> >      freq (321 -321) =        317.0  [cm-1]   --> A               I+R
> >      freq (322 -322) =        370.8  [cm-1]   --> A               I+R
> >      freq (323 -323) =        377.3  [cm-1]   --> A               I+R
> >      freq (324 -324) =        398.3  [cm-1]   --> A               I+R
> >      freq (325 -325) =        417.8  [cm-1]   --> A               I+R
> >      freq (326 -326) =        468.2  [cm-1]   --> A               I+R
> >      freq (327 -327) =        659.0  [cm-1]   --> A               I+R
> >      freq (328 -328) =       1096.6  [cm-1]   --> A               I+R
> >      freq (329 -329) =       1795.5  [cm-1]   --> A               I+R
> >      freq (330 -330) =       2199.3  [cm-1]   --> A               I+R
> >
> >
> > ph.x input file:
> >
> > phonon calculation at Gamma point.
> > &inputph
> >   outdir = './outdir'
> >   prefix = 'HS'
> >   tr2_ph = 1.0d-09
> >   epsil = .false.
> >   amass(1) = 58.69340
> >   amass(2) = 30.97376
> >   amass(3) = 1.00784
> >   amass(4) = 32.065
> >   fildyn = 'HS.dyn'
> >
> > alpha_mix(1)=0.1
> >
> >  recover=.true
> >   nogg = .true
> >   nat_todo = 5
> >
> > /
> > 0.0 0.0 0.0
> >
> > 1 2 37 46 54
> >
> >
> >
> > scf input file:
> >
> > &CONTROL
> >     calculation   = "scf"
> > prefix = 'HS'
> >     outdir = './outdir'
> >     pseudo_dir = '/home/'
> > restart_mode = 'from_scratch'
> >     forc_conv_thr =  1.0e-03
> > etot_conv_thr = 1e-04
> >     nstep         = 999
> > /
> > &SYSTEM
> > ibrav  =  0
> >     ecutrho                   =  200
> >     ecutwfc                   =  25
> >     nat                       = 110
> >     ntyp                      = 4
> > occupations='smearing',smearing='gaussian',degauss=0.005
> > vdw_corr = 'DFT-D2'
> >      nspin = 2
> >  starting_magnetization(1)=  0.01
> > /
> > &ELECTRONS
> >     conv_thr         = 1e-8
> >     electron_maxstep = 200
> > mixing_mode ='local-TF'
> >     mixing_beta      =  0.3
> > /
> > &IONS
> > /
> > K_POINTS {automatic}
> > 3 3 1     0 0 0
> > ATOMIC_SPECIES
> > Ni 58.69340 Ni.pbe-n-rrkjus_psl.0.1.UPF
> > P 30.97376 P.pbe-n-rrkjus_psl.1.0.0.UPF
> > H 1.00784 H.pbe-rrkjus_psl.0.1.UPF
> > S  32.065      S.pbe-n-rrkjus_psl.1.0.0.UPF
> > CELL_PARAMETERS {angstrom}
> >         11.76538354           0.0000000000         0.0000000000
> >        -5.8826917709        10.189121032         0.0000000000
> >         0.0000000000         0.0000000000        30.993869056
> > ATOMIC_POSITIONS (angstrom)
> > H        0.879694621   3.392266427  10.708999692
> > S        2.266698845   3.396363162  10.560733430
> > Ni      -2.744571590   4.755054131   0.244939179
> > Ni       3.134031329   1.363792691   0.248008546
> > .
> > .
> > .
> > P       -1.060403962   1.841094610   1.604930623
> > P       -3.921453199   6.792156181   0.000000000    0   0   0
> > P        1.960697149   3.396027080   0.000000000    0   0   0
> > P        7.842906399   0.000000000   0.000000000    0   0   0
> >
> >
> > regards
> >
> >
> > _______________________________________________
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> > users mailing list users at lists.quantum-espresso.org
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