MULLIKEN CHARGE

Josip Lovrić josip7... at gmail.com
Mon Dec 19 19:05:55 CET 2016


Sorry for not responding immediately, I was of computer for some time. 
Published article on which I am referring is this 
http://pubs.acs.org/doi/suppl/10.1021/jz3014985 and they give results for 
BASIS PSEUDOPOTENTIAL. I have deleted my all electron calculations. I will 
repeat them if necessary.
Now when I wanted to copy paste their results here I see that they actually 
performed gas phase calculation with NO2 dimer +  water and HCl molecule.
So my comparison make no sense, sorry for wasting your time. Nevertheless 
this stays strange for me because I have also performed this calculation 
(cis dimer isolate) in Gaussian(basis downloaded from 
https://bse.pnl.gov/bse/portal) and charges are closed to one in paper.

No problem Matt, anyway I will try to implement your suggestions. 

Josip



On Monday, December 19, 2016 at 5:29:54 PM UTC+1, Matt W wrote:
>
> Also, your box is too small, and maybe you don't centre your molecule
>
>     &CELL
>       ABC 10.0 10.0 10.0
>       PERIODIC NONE
>     &END CELL
>     &COORD
>        N 2.233559   -3.621843    1.337023
>        O 2.067990   -2.527433    1.053663
>        O 3.021496   -3.912949    2.863941
>        N 3.415616   -2.732165    3.611083
>        O 3.805883   -1.768317    2.949635
>        O 3.319372   -2.851822    4.823878
>     &END
>     &TOPOLOGY
>        &CENTER_COORDINATES
>        &END
>     &END TOPOLOGY
>
> Try something like above and see if it helps.
>
> Matt
>
> On Monday, December 19, 2016 at 4:09:18 PM UTC, Josip Lovrić wrote:
>>
>> 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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