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

Bálint Aradi aradi at uni-bremen.de
Tue Nov 22 15:02:55 CET 2022


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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>      >      >
>      >      >             --
>      >      >             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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>      >     --
>      >     Dr. Bálint Aradi
>      >     Bremen Center for Computational Materials Science, University
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>     https://mailman.zfn.uni-bremen.de/cgi-bin/mailman/listinfo/dftb-plus-user <https://mailman.zfn.uni-bremen.de/cgi-bin/mailman/listinfo/dftb-plus-user>
> 
>     -- 
>     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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-- 
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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