[DFTB-Plus-User] How DFTB+ manages atomic charges?

giacomo buccella gek.buccella at gmail.com
Tue Nov 22 15:06:38 CET 2022


Ok, thank you very much for your help and patience.
Best regards

Giacomo

Il giorno mar 22 nov 2022 alle ore 15:03 Bálint Aradi <aradi at uni-bremen.de>
ha scritto:

> On 22.11.22 14:48, giacomo buccella wrote:
> > I'll with default mixer then, but what about the temperature? Why should
> > I increase it up to 1000 K when I want reaction dynamics at 300K?
>
> Because, this is the electronic temperature, not the ionic one, so its
> OK to have a different value from the actual ambient temperature.
> Consider it more as a tool to help you accelerating convergence. As long
> as it is not too high, the results should be OK. Your system will also
> converge with 300 K electronic temperature, but will need much more
> SCC-cycles. I doubt, that there will be a significant difference in the
> trajectories, though, but you should maybe test it.
>
> By the way, the convergence may become smoother, when the system has
> done a few steps already. If you are concerned about the high electronic
> temperature, do a few steps with it and restart then the MD with a lower
> one from there.
>
> One more remark: on my laptop the optimal nr. of threads is 2, I finish
> the same calculation in less than 4 minutes then. Your system is just
> too small to scale beyond 2 threads, so make sure, you do not run it on
> too many threads/cores. Make sure to set OMP_NUM_THREADS and/or the
> 'mpirun -n' parameter correctly.
>
> Best regards,
>
> Bálint
>
>
> >
> > Il giorno mar 22 nov 2022 alle ore 14:44 Bálint Aradi
> > <aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>> ha scritto:
> >
> >
> >      > Being aware that charge transfer reactions should be treated with
> >     other
> >      > methods, I am however trying to simulate the impact of different
> >     ions
> >      > with a polymeric surface (at 300 K).
> >      > Here's another issue: the runs are incredibly slow. This of
> >     course makes
> >      > me think I'm doing something wrong.
> >      > Can you please take a look and provide some tips to speed them up
> >      > (besides increasing the core number) ?
> >      > Please find attached an example of calculation, which performed
> only
> >      > 17-18 steps in 24h.
> >
> >     Your system converges quite slowly for some reaons. I've raised the
> >     temperature to 1000 K to ease convergence, set SccTolerance to he
> >     default value, used the default (Broyden) mixer with the default
> >     parameters. On my 6 years old laptop, I've managed so to run your
> >     system
> >     for 10 geometry steps within 5 minutes and 12 seconds (using 4
> threads)
> >     with the serial Conda-binary, so I should be able to do ca. 3000
> steps
> >     per day.
> >
> >     If it is considerable slower for you, you are either using too many
> >     threads/processes or your build is completely broken.
> >
> >     Best regards,
> >
> >     Bálint
> >
> >
> >      >
> >      > Many thanks
> >      > Best regards
> >      >
> >      > Giacomo
> >      >
> >      > Il giorno mar 22 nov 2022 alle ore 11:50 Bálint Aradi
> >      > <aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>
> >     <mailto:aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>>> ha
> scritto:
> >      >
> >      >     Just a quick note on this. Given the rather small size of our
> >      >     Hamiltonian (as compared to ab inito DFT calculations) and
> >     the fact,
> >      >     that we do not need to carry out integrations during the
> >     calculations,
> >      >     usually you don't gain much from running DFTB+ on multiple
> >     nodes with
> >      >     only a few hundreds of atoms. So please, always check the
> >     scalability
> >      >     (OpenMP threads or MPI processes) first and choose the number
> of
> >      >     threads
> >      >     or MPI processes accordingly. Otherwise you may end up with
> >     wasting
> >      >     computational resources and also your precious wall clock
> time.
> >      >
> >      >     Best regards,
> >      >
> >      >     Bálint
> >      >
> >      >
> >      >     On 17.11.22 14:19, giacomo buccella wrote:
> >      >      > Dear Charly,
> >      >      >
> >      >      > my sistem is nearly 350 atoms. It is not that big, but
> >     enough to
> >      >     be sort
> >      >      > of unaffordable without using parallel machines, since I
> >     need to run
> >      >      > tens of MD runs considering different starting
> >     configurations. I
> >      >     surely
> >      >      > can run one test with a single thread, just to check how
> >     much the
> >      >     result
> >      >      > is affected by using long-range corrections.
> >      >      > Many thanks for your support
> >      >      > Best regards
> >      >      >
> >      >      > Giacomo
> >      >      >
> >      >      > Il giorno gio 17 nov 2022 alle ore 14:13 Carlos R.
> >     Lien-Medrano
> >      >      > <cmedrano at uni-bremen.de <mailto:cmedrano at uni-bremen.de>
> >     <mailto:cmedrano at uni-bremen.de <mailto:cmedrano at uni-bremen.de>>
> >      >     <mailto:cmedrano at uni-bremen.de
> >     <mailto:cmedrano at uni-bremen.de> <mailto:cmedrano at uni-bremen.de
> >     <mailto:cmedrano at uni-bremen.de>>>> ha
> >      >     scritto:
> >      >      >
> >      >      >     Dear Giacomo,
> >      >      >
> >      >      >     I don't know the dimensions of your system but is it
> >     strictly
> >      >     needed
> >      >      >     that you run
> >      >      >     the calculation in parallel? Otherwise, you could give
> >     a chance
> >      >      >     performing the
> >      >      >     calculation just in one node using long-range
> corrections.
> >      >      >
> >      >      >     Best regards,
> >      >      >     Charly
> >      >      >
> >      >      >     El jue, 17 nov 2022 a las 7:02, giacomo buccella
> >      >      >     (<gek.buccella at gmail.com
> >     <mailto:gek.buccella at gmail.com> <mailto:gek.buccella at gmail.com
> >     <mailto:gek.buccella at gmail.com>>
> >      >     <mailto:gek.buccella at gmail.com
> >     <mailto:gek.buccella at gmail.com> <mailto:gek.buccella at gmail.com
> >     <mailto:gek.buccella at gmail.com>>>>)
> >      >     escribió:
> >      >      >
> >      >      >         Dear Bálint,
> >      >      >         thanks for the kind reply. I've just tried to
> >     implement Long
> >      >      >         Range corrections, but it seems that this option
> >     is not yet
> >      >      >         available when you run with mpi threads:
> >      >      >
> >      >      >         **********************
> >      >      >         ...
> >      >      >         Starting initialization...
> >      >      >
> >      >
> >
>  --------------------------------------------------------------------------------
> >      >      >         WARNING!
> >      >      >         -> Dipole printed for a charged system : origin
> >     dependent
> >      >     quantity
> >      >      >         WARNING!
> >      >      >         -> Dipole printed for extended system : value
> >     printed is not
> >      >      >         well defined
> >      >      >         ERROR!
> >      >      >         -> Range separated calculations do not work with
> >     MPI yet
> >      >      >
> >      >      >         *********************
> >      >      >         Do you have any other advice?
> >      >      >
> >      >      >         Many thanks
> >      >      >         best regards
> >      >      >
> >      >      >         Giacomo
> >      >      >
> >      >      >         Il giorno gio 17 nov 2022 alle ore 07:54 Bálint
> Aradi
> >      >      >         <aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>
> >     <mailto:aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>>
> >      >     <mailto:aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>
> >     <mailto:aradi at uni-bremen.de <mailto:aradi at uni-bremen.de>>>> ha
> scritto:
> >      >      >
> >      >      >             Dear Giacomo,
> >      >      >
> >      >      >             this not DFTB related, but is common for all
> DFT
> >      >     approaches:
> >      >      >             DFT(B)
> >      >      >             methods tend to delocalize charges. You have
> >     one common
> >      >      >             Fermi level in
> >      >      >             the system, and if you have degenerated (or
> >      >      >             quasi-degenerated) states,
> >      >      >             such as likely the atomic level of the N atom
> >     and the
> >      >     VBM of
> >      >      >             your
> >      >      >             surface, charge will be distributed between
> them,
> >      >      >             independently, how far
> >      >      >             they are spatially from each other.
> >      >      >
> >      >      >             Charge transfer reactions are usually
> calculated
> >      >     using range
> >      >      >             separated
> >      >      >             functionals (which you have in DFTB as well).
> >      >     Alternatively,
> >      >      >             one can
> >      >      >             also enforce a charge distribution via
> constraint
> >      >     DFT, but
> >      >      >             we don't have
> >      >      >             constrained DFTB in the official version yet.
> >      >      >
> >      >      >             Best regards,
> >      >      >
> >      >      >             Bálint
> >      >      >
> >      >      >
> >      >      >             On 16.11.22 11:16, giacomo buccella wrote:
> >      >      >              > Hi everyone, I'm asking for help about an
> >     issue to
> >      >     which
> >      >      >             I don't find
> >      >      >              > any answer in the manual.
> >      >      >              > I'm interested in simulating a chemical
> >     system with
> >      >      >             excess (or lack) of
> >      >      >              > charge on certain particular atoms.
> >      >      >              > The problem is that the after a single MD
> step
> >      >      >             (timestep=0.5 fs), the
> >      >      >              > charge is already delocalized among all
> >     atoms in the
> >      >      >             cell. This occurs
> >      >      >              > even if I'm simulating an ion approaching a
> >      >     distant surface.
> >      >      >              >
> >      >      >              > Example:
> >      >      >              > I want to simulate the ion N(+) approaching
> a
> >      >     surface, so
> >      >      >             I set the
> >      >      >              > initial charge of N atom = +1.000 :
> >      >      >              >
> >      >      >              > InitialCharges = {
> >      >      >              > AtomCharge = {
> >      >      >              > Atoms = N
> >      >      >              > ChargePerAtom = +1.0000
> >      >      >              > }
> >      >      >              > }
> >      >      >              >
> >      >      >              > therefore, I expect that at the beginning
> >     of the
> >      >      >             simulation the number
> >      >      >              > of electrons associated with N would be
> 5-1=4.
> >      >      >              > Well, after a single MD step, its charge is
> >      >     already about
> >      >      >             4.9, even if
> >      >      >              > it is still 10 AA away from other atoms in
> >     the system
> >      >      >             with which it
> >      >      >              > could interact.
> >      >      >              >
> >      >      >              > My question is: how is this possible? is it
> >     something
> >      >      >             related to the way
> >      >      >              > DFTB+ manages the charge distribution? Do I
> >     need a
> >      >      >             time-dependent
> >      >      >              > calculation for this?
> >      >      >              > Any suggestion would be really appreciated
> >      >      >              > Many thanks
> >      >      >              >
> >      >      >              > Giacomo
> >      >      >              >
> >      >      >              >
> >      >      >              >
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> >      >      >
> >      >
> >
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> >      >      >
> >      >      >             --
> >      >      >             Dr. Bálint Aradi
> >      >      >             Bremen Center for Computational Materials
> Science,
> >      >      >             University of Bremen
> >      >      > http://www.bccms.uni-bremen.de/cms/people/b-aradi/
> >     <http://www.bccms.uni-bremen.de/cms/people/b-aradi/>
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> >      >      >
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> >      >      >
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> >      >
> >      >     --
> >      >     Dr. Bálint Aradi
> >      >     Bremen Center for Computational Materials Science, University
> >     of Bremen
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> >     Bremen Center for Computational Materials Science, University of
> Bremen
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> Dr. Bálint Aradi
> Bremen Center for Computational Materials Science, University of Bremen
> http://www.bccms.uni-bremen.de/cms/people/b-aradi/
>
>
> _______________________________________________
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> https://mailman.zfn.uni-bremen.de/cgi-bin/mailman/listinfo/dftb-plus-user
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