[CPMD-list] population analysis mulliken

Axel Kohlmeyer axel.kohlmeyer at theochem.ruhr-uni-bochum.de
Mon May 30 18:31:27 CEST 2005


On Mon, 30 May 2005, zhen gong wrote:

ZG>   hi, everyone!
ZG>    I have a problem about the population analysis mulliken.

dear zhen gong,

there are a couple of issues with your input, that are
unrelated to the population analysis. i suspect, that 
you do not have a proper wavefunction to boot.

before you can do a population analysis, you need
a good wavefunction. assuming, that you have done the
previous wavefunction optimization with the same
parameters in your input, you won't get it.

ZG> This is a test example, but the results is incredible, the "unassigned charge" is 14.
ZG> Do I have a mistake? What's the population analysis results mean?
ZG> 
ZG> 
ZG>  ** &CPMD                                                                    **
ZG>  **   MIRROR                                                                 **
ZG>  **   RESTART WAVEFUCNTION LATEST                                            **
ZG>  **   PROPERTIES                                                             **
ZG>  **   CONVERGENCE ORBITALS                                                   **
ZG>  **    1.0D-3

this is _far_ too large. to analyse a wavefunction,
you need a well converged wavefunction (1.d6-1.d8,
the lower). the default value (1.d5) is good enough
to start a CP-MD, where your wavefunction will oscillate
around the 'real' optimal structure, anyways.
                                                                **
ZG>  **   ODIIS NO_RESET=200                                                     **
ZG>  **    10                                                                    **

since you include a semicore pseudopotentials, 
convergence will be somewhat tricky. you should
try with a smaller DIIS vector (e.g. 5) or use
PCG MINIMIZE.

ZG>  **   MAXSTEP                                                                **
ZG>  **    3000                                                                  **

ZG>  ** &END                                                                     **
ZG>  **                                                                          **
ZG>  **  &SYSTEM                                                                 **
ZG>  **    ANGSTROM                                                              **
ZG>  **    CHARGE                                                                **
ZG>  **      0                                                                   **

hmmm. you have Na atoms in your system,
but use charge 0 and don't do an open shell
calculation, i would (naiively?) expect, that you 
either have to set charge to 4.0 or do an LSD 
calcuation with MULTIPLICITY 5.

ZG>  **    SYMMETRY                                                              **
ZG>  **      1                                                                   **
ZG>  **    CELL                                                                  **
ZG>  **       7.0 1.0 1.0 0.0 0.0 0.0                                            **

with a cell of this size, you probably need to add
 TESR
   1
to have a better convergence of the ewald sum.

ZG>  **    CUTOFF                                                                **
ZG>  **       70.0                                                               **

i don't think that 70ry is a sufficient cutoff
for a sodium semicore pseudopotential. you may
get 'away' with ~90.0 for an md (hoping for cancellation
of errors), but for analysing the wavefunction
you probably need at least 100ry, maybe 120ry.

[...]

ZG>  **    1.735  -3.545   0.479                                                 **

ZG>  ** *O_MT_HCTH.psp                                                           **

you should add the KLEINMAN-BYLANDER 
flag here...

ZG>  ** *Na_MT_HCTH_SEMI.psp                                                     **

... and here.

ZG>  **   LMAX=P                                                                 **

also the &INFO section of this file tells
you to use LOC=S here


ZG>  **    4                                                                     **
ZG>  **   -1.105   1.821  -0.987                                                 **
ZG>  **    1.275   1.207   3.051                                                 **
ZG>  **   -0.865  -0.893   0.042                                                 **
ZG>  **   -3.057   0.840   1.147                                                 **
ZG>  ** &END                                                                     **
ZG>  **                                                                          **
ZG>  ** &DFT                                                                     **
ZG>  **   FUNCTIONAL HCTH                                                        **
ZG>  ** &END                                                                     **
ZG>  **                                                                          **
ZG>  **                                                                          **
ZG>  **                                                                          **

finally, you should, for the sake of consistency
poject onto the pseudowavefunctions, as they are
contained in the pseudopotential files. for the
semi-core sodium potential, this makes less sense,
since you don't have a wavefunction for the valence s
state. so your &BASIS section should look like this:

&BASIS
 PSEUDO AO 1
  0
 PSEUDO AO 2
  0 1
 SKIP
&END

ZG>   31    Na              1.048         1.141         0.822
ZG>   UNASSIGNED CHARGE    14.061        14.061

with all those changes, even without a well converged
wavefunction (i just made a quick check). the amount
of unassigned charge will easily go below 2. and your
results should make much more sense, too.

regards,
	axel.


ZG> ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡zhen gong
ZG> ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡legend_gongzhen at hotmail.com
ZG> ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡2005-05-30
ZG> 
ZG> 
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ZG> http://cpmd.org/mailman/listinfo/cpmd-list
ZG> 
ZG> 

-- 

=======================================================================
Dr. Axel Kohlmeyer   e-mail: axel.kohlmeyer at theochem.ruhr-uni-bochum.de
Lehrstuhl fuer Theoretische Chemie          Phone: ++49 (0)234/32-26673
Ruhr-Universitaet Bochum - NC 03/53         Fax:   ++49 (0)234/32-14045
D-44780 Bochum  http://www.theochem.ruhr-uni-bochum.de/~axel.kohlmeyer/
=======================================================================
If you make something idiot-proof, the universe creates a better idiot.




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