MULLIKEN CHARGE

Josip Lovrić josip7... at gmail.com
Mon Dec 19 17:09:18 CET 2016


Dear Matt,

I totally agree with you and I am aware of fact that atomic charge are just 
model. 
Maybe I was not clear enough but my problem is that charges are not 
consistent with published values.

P.S. input files are named "*_all_electrons*". This is mistake, calculation 
is not all electron, it is a relict from previous calculation.

Josip

On Monday, December 19, 2016 at 5:03:50 PM UTC+1, Matt W wrote:
>
> Hi Josip,
>
> Mulliken charges are not real observables - they are strongly dependent on 
> the basis set, and they do not converge as you make the basis set complete. 
> Check a quantum chemistry textbook for a good discussion ('Computational 
> Chemistry', Errol Lewars for instance).
>
> Something more quantitative can come from something like Bader charge 
> analysis (which needs external processing of a total_charge_density cube 
> file).
>
> Matt
>
> On Monday, December 19, 2016 at 3:56:55 PM UTC, Josip Lovrić wrote:
>>
>> Dear CP2K community,
>>
>> Recently I was working on NO2-dimer and now I need help from you. Thing 
>> is that I am running gas phase calculation of NO2 cis-dimer. After program 
>> successfully  finish GEOMETRIC OPTIMIZATION output configuration is 
>> consistent with already published papers. Problem is in the MULLIKEN 
>> charges. Charges are too small and not consistent with published values(I 
>> am using same basis set).
>>
>> !-----------------------------------------------------------------------------!
>>                      Mulliken Population Analysis
>>
>>  #  Atom  Element  Kind  Atomic population                           Net 
>> charge
>>        1     N        1          4.968657                             
>>  0.031343
>>        2     O        2          5.852787                             
>>  0.147213
>>        3     O        2          6.191534                             
>> -0.191534
>>        4     N        1          4.928901                             
>>  0.071099
>>        5     O        2          6.056358                             
>> -0.056358
>>        6     O        2          6.001764                             
>> -0.001764
>>  # Total charge                             34.000000                 
>>  0.000000
>>
>>
>>  !-----------------------------------------------------------------------------!
>> I am using BLYP functional with dispersion corrections and TZV2P basis 
>> set with pseudo-potentials. Charges are becoming more physical when 
>> performing all electron calculation, they increase for factor ~10. 
>> For DZVP basis set charges increase little, but still to low:
>>
>>  !-----------------------------------------------------------------------------!
>>                      Mulliken Population Analysis
>>
>>  #  Atom  Element  Kind  Atomic population                           Net 
>> charge
>>        1     N        1          4.951639                             
>>  0.048361
>>        2     O        2          5.822911                             
>>  0.177089
>>        3     O        2          6.202144                             
>> -0.202144
>>        4     N        1          4.858609                             
>>  0.141391
>>        5     O        2          6.103330                             
>> -0.103330
>>        6     O        2          6.061367                             
>> -0.061367
>>  # Total charge                             34.000000                 
>> -0.000000
>>
>>
>>  !-----------------------------------------------------------------------------!
>>   Am I doing something wrong? Do you have any explanation for this 
>> results?
>> I would really appreciate. 
>>
>> I am putting in attachment my input and output files. 
>>
>> Best wishes
>> Josip
>>
>
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