[CP2K-user] dimension inconsistency of the overlap and MO coefficients

Xiaoming Wang wxia... at gmail.com
Fri Oct 12 15:47:43 UTC 2018


Hi Vladimir,

Thanks for your suggestions.  

Best,
Xiaoming

For my applications, however, I do need the OT method. 
So I cannot use ADDED_MOS. 

On Friday, October 12, 2018 at 10:04:18 AM UTC-4, Vladimir Rybkin wrote:
>
> Dear Xiaoming,
>
> you need to do the following:
> 1) use DIAGONALIZATION ins SCF
> 2) in SCF use ADDED_MOS #very large number
>
> Yours,
>
> Vladimir
>
> пятница, 12 октября 2018 г., 14:53:59 UTC+2 пользователь Xiaoming Wang 
> написал:
>>
>> Hi Vladimir,
>>
>> I'm sorry I made a mistake. I mean could the overlap matrix be 
>> transformed to cartesian coordinates? Because I only have the MO of LUMO 
>> printed in cartesian coordinates.
>>
>> Best,
>> Xiaoming 
>>
>> On Friday, October 12, 2018 at 8:48:45 AM UTC-4, Vladimir Rybkin wrote:
>>>
>>> Hi Xiaoming,
>>>
>>> overlap matrix is already in spherical Gaussians. The overlap is taken 
>>> between basis functions (AO), not between MO(s). It is calculated before 
>>> any MOs are obtained.
>>>
>>> Yours,
>>>
>>> Vladimir
>>>
>>> пятница, 12 октября 2018 г., 14:34:43 UTC+2 пользователь Xiaoming Wang 
>>> написал:
>>>>
>>>> Hi Vladimir,
>>>>
>>>> Thanks for your confirmation. Yes, with Cartesian off, the dimensions 
>>>> are consistent now. If cp2k does not print MO of vacant state, then is it 
>>>> possible to transform the overlap matrix to spherical coordinates?
>>>>
>>>> Best,
>>>> Xiaoming
>>>>
>>>> On Friday, October 12, 2018 at 8:18:30 AM UTC-4, Vladimir Rybkin wrote:
>>>>>
>>>>> Dear Xiaoming,
>>>>>
>>>>> thank you for the data. I don't see any inconsistency now. You get 52 
>>>>> with Cartesian off and 54 with Cartesian on. Turning Cartesian off you can 
>>>>> now multiply your C with your S. Isn't that what you want? Unfortunately, I 
>>>>> can't comment on why orbital #5 is not printed. Perhaps, that is due to the 
>>>>> fact that it is vacant.
>>>>>
>>>>> Yours,
>>>>>
>>>>> Vladimir
>>>>>
>>>>> пятница, 12 октября 2018 г., 13:47:35 UTC+2 пользователь Xiaoming Wang 
>>>>> написал:
>>>>>>
>>>>>> Hi Vladimir,
>>>>>>
>>>>>> Thanks for you reply.
>>>>>>
>>>>>> My input of the print part is:
>>>>>>
>>>>>> ------------
>>>>>>
>>>>>>     &MO
>>>>>>
>>>>>>       EIGENVALUES
>>>>>>
>>>>>>       EIGENVECTORS
>>>>>>
>>>>>>       CARTESIAN
>>>>>>
>>>>>>       FILENAME mos
>>>>>>
>>>>>>       MO_INDEX_RANGE 4 5
>>>>>>
>>>>>>       OCCUPATION_NUMBERS
>>>>>>
>>>>>>       &EACH
>>>>>>
>>>>>>        QS_SCF 0
>>>>>>
>>>>>>       &END EACH
>>>>>>
>>>>>>      &END MO
>>>>>>
>>>>>> --------------
>>>>>>
>>>>>>
>>>>>> With CARTESIAN on, I get
>>>>>>
>>>>>>
>>>>>> ----------------
>>>>>>
>>>>>>  MO EIGENVALUES, MO OCCUPATION NUMBERS, AND CARTESIAN MO EIGENVECTORS
>>>>>>
>>>>>>
>>>>>>                               4            5
>>>>>>
>>>>>>                           -0.260963    -0.034173
>>>>>>
>>>>>>
>>>>>>                            2.000000     0.000000
>>>>>>
>>>>>>
>>>>>>      1     1  O  2s        0.000000     0.236782
>>>>>>
>>>>>>      2     1  O  3s        0.000000    -0.090781
>>>>>>
>>>>>>      3     1  O  4s        0.000000    -0.240258
>>>>>>
>>>>>>      4     1  O  3px      -0.917807    -0.000000
>>>>>>
>>>>>>      5     1  O  3py      -0.000000    -0.000000
>>>>>>
>>>>>>      6     1  O  3pz       0.000000    -0.238095
>>>>>>
>>>>>>      7     1  O  4px       0.020934    -0.000000
>>>>>>
>>>>>>      8     1  O  4py       0.000000    -0.000000
>>>>>>
>>>>>>      9     1  O  4pz      -0.000000     0.013849
>>>>>>
>>>>>>     10     1  O  5px      -0.003042     0.000000
>>>>>>
>>>>>>     11     1  O  5py       0.000000     0.000000
>>>>>>
>>>>>>     12     1  O  5pz      -0.000000     0.099980
>>>>>>
>>>>>>     13     1  O  3dx2     -0.000000     0.000099
>>>>>>
>>>>>>     14     1  O  3dxy     -0.000000    -0.000000
>>>>>>
>>>>>>     15     1  O  3dxz     -0.005256    -0.000000
>>>>>>
>>>>>>     16     1  O  3dy2     -0.000000     0.000744
>>>>>>
>>>>>>     17     1  O  3dyz      0.000000    -0.000000
>>>>>>
>>>>>>     18     1  O  3dz2      0.000000    -0.000844
>>>>>>
>>>>>>     19     1  O  4dx2     -0.000000     0.000357
>>>>>>
>>>>>>     20     1  O  4dxy      0.000000    -0.000000
>>>>>>
>>>>>>     21     1  O  4dxz     -0.022359     0.000000
>>>>>>
>>>>>>     22     1  O  4dy2      0.000000     0.004105
>>>>>>
>>>>>>     23     1  O  4dyz     -0.000000     0.000000
>>>>>>
>>>>>>     24     1  O  4dz2      0.000000    -0.004463
>>>>>>
>>>>>>     25     1  O  5s       -0.000000    -0.011663
>>>>>>
>>>>>>     26     1  O  5px       0.024750    -0.000000
>>>>>>
>>>>>>     27     1  O  5py      -0.000000     0.000000
>>>>>>
>>>>>>     28     1  O  5pz       0.000000    -0.077018
>>>>>>
>>>>>>
>>>>>>     29     2  H  1s        0.000000    -0.116793
>>>>>>
>>>>>>     30     2  H  2s        0.000000    -0.003374
>>>>>>
>>>>>>     31     2  H  3s       -0.000000     0.197029
>>>>>>
>>>>>>     32     2  H  2px       0.011575    -0.000000
>>>>>>
>>>>>>     33     2  H  2py       0.000000     0.008716
>>>>>>
>>>>>>     34     2  H  2pz      -0.000000    -0.004748
>>>>>>
>>>>>>     35     2  H  3px       0.028901    -0.000000
>>>>>>
>>>>>>     36     2  H  3py       0.000000     0.013894
>>>>>>
>>>>>>     37     2  H  3pz      -0.000000    -0.010138
>>>>>>
>>>>>>     38     2  H  4s       -0.000000     0.421270
>>>>>>
>>>>>>     39     2  H  4px       0.026994     0.000000
>>>>>>
>>>>>>     40     2  H  4py       0.000000     0.041403
>>>>>>
>>>>>>     41     2  H  4pz      -0.000000    -0.044975
>>>>>>
>>>>>>
>>>>>>     42     3  H  1s        0.000000    -0.116793
>>>>>>
>>>>>>     43     3  H  2s       -0.000000    -0.003374
>>>>>>
>>>>>>     44     3  H  3s        0.000000     0.197029
>>>>>>
>>>>>>     45     3  H  2px       0.011575    -0.000000
>>>>>>
>>>>>>     46     3  H  2py       0.000000    -0.008716
>>>>>>
>>>>>>     47     3  H  2pz      -0.000000    -0.004748
>>>>>>
>>>>>>     48     3  H  3px       0.028901    -0.000000
>>>>>>
>>>>>>     49     3  H  3py      -0.000000    -0.013894
>>>>>>
>>>>>>     50     3  H  3pz      -0.000000    -0.010138
>>>>>>
>>>>>>     51     3  H  4s        0.000000     0.421270
>>>>>>
>>>>>>     52     3  H  4px       0.026994     0.000000
>>>>>>
>>>>>>     53     3  H  4py       0.000000    -0.041403
>>>>>>
>>>>>>     54     3  H  4pz       0.000000    -0.044975
>>>>>>
>>>>>>
>>>>>>
>>>>>>   Fermi energy:                -0.260963
>>>>>>
>>>>>>
>>>>>>   HOMO-LUMO gap:                0.226790 =   6.17 eV
>>>>>> ---------------------------------------
>>>>>>
>>>>>> However, with CARTESIAN OFF, I get only the orbital #4:
>>>>>>
>>>>>> ----------------------------------------
>>>>>>
>>>>>>  MO EIGENVALUES, MO OCCUPATION NUMBERS, AND SPHERICAL MO EIGENVECTORS
>>>>>>
>>>>>>
>>>>>>                               4
>>>>>>
>>>>>>                           -0.260963
>>>>>>
>>>>>>
>>>>>>                            2.000000
>>>>>>
>>>>>>
>>>>>>      1     1  O  2s        0.000000
>>>>>>
>>>>>>      2     1  O  3s        0.000000
>>>>>>
>>>>>>      3     1  O  4s        0.000000
>>>>>>
>>>>>>      4     1  O  3py      -0.000000
>>>>>>
>>>>>>      5     1  O  3pz       0.000000
>>>>>>
>>>>>>      6     1  O  3px      -0.917807
>>>>>>
>>>>>>      7     1  O  4py       0.000000
>>>>>>
>>>>>>      8     1  O  4pz      -0.000000
>>>>>>
>>>>>>      9     1  O  4px       0.020934
>>>>>>
>>>>>>     10     1  O  5py       0.000000
>>>>>>
>>>>>>     11     1  O  5pz      -0.000000
>>>>>>
>>>>>>     12     1  O  5px      -0.003042
>>>>>>
>>>>>>     13     1  O  3d-2     -0.000000
>>>>>>
>>>>>>     14     1  O  3d-1      0.000000
>>>>>>
>>>>>>     15     1  O  3d0       0.000000
>>>>>>
>>>>>>     16     1  O  3d+1     -0.005256
>>>>>>
>>>>>>     17     1  O  3d+2     -0.000000
>>>>>>
>>>>>>     18     1  O  4d-2      0.000000
>>>>>>
>>>>>>     19     1  O  4d-1     -0.000000
>>>>>>
>>>>>>     20     1  O  4d0       0.000000
>>>>>>
>>>>>>     21     1  O  4d+1     -0.022359
>>>>>>
>>>>>>     22     1  O  4d+2     -0.000000
>>>>>>
>>>>>>     23     1  O  5s       -0.000000
>>>>>>
>>>>>>     24     1  O  5py      -0.000000
>>>>>>
>>>>>>     25     1  O  5pz       0.000000
>>>>>>
>>>>>>     26     1  O  5px       0.024750
>>>>>>
>>>>>>
>>>>>>     27     2  H  1s        0.000000
>>>>>>
>>>>>>     28     2  H  2s        0.000000
>>>>>>
>>>>>>     29     2  H  3s       -0.000000
>>>>>>
>>>>>>     30     2  H  2py       0.000000
>>>>>>
>>>>>>     31     2  H  2pz      -0.000000
>>>>>>
>>>>>>     32     2  H  2px       0.011575
>>>>>>
>>>>>>     33     2  H  3py       0.000000
>>>>>>
>>>>>>     34     2  H  3pz      -0.000000
>>>>>>
>>>>>>     35     2  H  3px       0.028901
>>>>>>
>>>>>>     36     2  H  4s       -0.000000
>>>>>>
>>>>>>     37     2  H  4py       0.000000
>>>>>>
>>>>>>     38     2  H  4pz      -0.000000
>>>>>>
>>>>>>     39     2  H  4px       0.026994
>>>>>>
>>>>>>
>>>>>>     40     3  H  1s        0.000000
>>>>>>
>>>>>>     41     3  H  2s       -0.000000
>>>>>>
>>>>>>     42     3  H  3s        0.000000
>>>>>>
>>>>>>     43     3  H  2py       0.000000
>>>>>>
>>>>>>     44     3  H  2pz      -0.000000
>>>>>>
>>>>>>     45     3  H  2px       0.011575
>>>>>>
>>>>>>     46     3  H  3py      -0.000000
>>>>>>
>>>>>>     47     3  H  3pz      -0.000000
>>>>>>
>>>>>>     48     3  H  3px       0.028901
>>>>>>
>>>>>>     49     3  H  4s        0.000000
>>>>>>
>>>>>>     50     3  H  4py       0.000000
>>>>>>
>>>>>>     51     3  H  4pz       0.000000
>>>>>>
>>>>>>     52     3  H  4px       0.026994
>>>>>>
>>>>>>
>>>>>>
>>>>>>   Fermi energy:                -0.260963
>>>>>>
>>>>>> -----------------------------
>>>>>>
>>>>>>
>>>>>> Why the MO #5 is not printed in spherical coordinate?
>>>>>>
>>>>>>
>>>>>> Best,
>>>>>>
>>>>>> Xiaoming
>>>>>>
>>>>>> On Friday, October 12, 2018 at 5:51:08 AM UTC-4, Vladimir Rybkin 
>>>>>> wrote:
>>>>>>>
>>>>>>> Hi Xiaoming,
>>>>>>>
>>>>>>> it is. I mean that by default it is not printed, only the basis is. 
>>>>>>> So, please attach your input/output: this will help to stay on equal 
>>>>>>> footing.
>>>>>>>
>>>>>>> Yours,
>>>>>>>
>>>>>>> Vladimir
>>>>>>>
>>>>>>> четверг, 11 октября 2018 г., 16:26:57 UTC+2 пользователь Xiaoming 
>>>>>>> Wang написал:
>>>>>>>>
>>>>>>>> Hi Vladimir,
>>>>>>>>
>>>>>>>> Are you saying the option of printing MOs with eigenvector on is 
>>>>>>>> not printing the MO coefficients?
>>>>>>>>
>>>>>>>> Best,
>>>>>>>> Xiaoming
>>>>>>>>
>>>>>>>> On Thursday, October 11, 2018 at 9:36:49 AM UTC-4, Vladimir Rybkin 
>>>>>>>> wrote:
>>>>>>>>>
>>>>>>>>> Dear Xiaoming,
>>>>>>>>>
>>>>>>>>> by default CP2K does not print MO coefficients. It prints the 
>>>>>>>>> basis, which is Cartesian (e.i. 6 d orbitals instead of 5). So, 
>>>>>>>>> input/output would be helpful.
>>>>>>>>>
>>>>>>>>> Yours,
>>>>>>>>>
>>>>>>>>> Vladimir
>>>>>>>>>
>>>>>>>>> четверг, 11 октября 2018 г., 15:24:16 UTC+2 пользователь Xiaoming 
>>>>>>>>> Wang написал:
>>>>>>>>>>
>>>>>>>>>> Hi,
>>>>>>>>>>
>>>>>>>>>> I just missed one thing. The MOs could also be printed with 
>>>>>>>>>> spherical coordinates. Then, it should be consistent.
>>>>>>>>>>
>>>>>>>>>> Best,
>>>>>>>>>> Xiaoming
>>>>>>>>>>
>>>>>>>>>> On Thursday, October 11, 2018 at 9:21:56 AM UTC-4, Xiaoming Wang 
>>>>>>>>>> wrote:
>>>>>>>>>>>
>>>>>>>>>>> Hi Vladimir,
>>>>>>>>>>>
>>>>>>>>>>> Thanks for your reply. I'm wondering why the eigenvectors and 
>>>>>>>>>>> overlap are not using the same basis (or with same basis but different 
>>>>>>>>>>> coordinates).
>>>>>>>>>>>
>>>>>>>>>>> Best,
>>>>>>>>>>> Xiaoming
>>>>>>>>>>>
>>>>>>>>>>> On Thursday, October 11, 2018 at 4:28:32 AM UTC-4, Vladimir 
>>>>>>>>>>> Rybkin wrote:
>>>>>>>>>>>>
>>>>>>>>>>>> Dear Xiaoming,
>>>>>>>>>>>>
>>>>>>>>>>>> the 6 d orbitals correspond to the six components in the 
>>>>>>>>>>>> Cartesian coordinates, whereas 5 d orbitals are the same expressed is 
>>>>>>>>>>>> spherical coordinates. The coordinate transformation is involved in 
>>>>>>>>>>>> between. 
>>>>>>>>>>>>
>>>>>>>>>>>> Yours,
>>>>>>>>>>>>
>>>>>>>>>>>> Vladimir
>>>>>>>>>>>>
>>>>>>>>>>>> среда, 10 октября 2018 г., 16:16:56 UTC+2 пользователь Xiaoming 
>>>>>>>>>>>> Wang написал:
>>>>>>>>>>>>>
>>>>>>>>>>>>> Hello,
>>>>>>>>>>>>>
>>>>>>>>>>>>> I'd like to check the equation C^T S C = 1, where C is MO 
>>>>>>>>>>>>> coefficient and S the overlap matrix. 
>>>>>>>>>>>>> However, for my test calculation, C is 54*1 while S is 52*52. 
>>>>>>>>>>>>> I checked the basis details, for the
>>>>>>>>>>>>> MO coefficient, there are 6 d orbitals 
>>>>>>>>>>>>> (dx2,dxy,dxz,dy2,dyz,dz2), while for the overlap matrix,
>>>>>>>>>>>>> only 5 d orbitals (d-2,d-1,d0,d+1,d+2) are printed. Why is 
>>>>>>>>>>>>> like that? Am I missing something?
>>>>>>>>>>>>>
>>>>>>>>>>>>> Best,
>>>>>>>>>>>>> Xiaoming 
>>>>>>>>>>>>>
>>>>>>>>>>>>
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