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

Vladimir Rybkin rybk... at gmail.com
Mon Oct 15 08:38:32 UTC 2018


Dear Xiaoming,

I believe that for no application does one need to check CSC=1. If you do 
it for fun than you might as well try diagonalization once.

Yours,

Vladimir

пятница, 12 октября 2018 г., 17:47:43 UTC+2 пользователь Xiaoming Wang 
написал:
>
> 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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