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

Vladimir Rybkin rybk... at gmail.com
Fri Oct 12 14:04:18 UTC 2018


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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