[CP2K:5015] Periodic RESP charges for paracetamol form I crystal

Dorothea Golze dorothe... at googlemail.com
Sat Mar 1 20:42:42 UTC 2014


Hi Mike  and Carlos

Yes, this problem is indeed taken care of. My implementation takes this
into account. It is working since version 2.4.

Regards,
Dorothea



2014-03-01 21:29 GMT+01:00 mbellucci <mbell... at gmail.com>:

>
> Hi Carlos,
>
> Thank you for your reply.  I have seen your paper before and I saw that
> you mentioned it on another thread related to periodic RESP fitting.  I am
> also not familiar with the inner workings of CP2K, but in the previous
> thread related to periodic RESP fitting, someone (Dorothea Golze) mentioned
> that the problem you identified in your paper is taken care of in the
> periodic RESP fit in the current version of CP2K.  Based on the version
> history of CP2K, it appears the last time any changes related to the RESP
> fitting was made was in version 2.4.  Since I'm using version 2.5 of CP2K,
> I'm assuming that it should work and the problem you mention is taken into
> account.
>
> Mike
>
>
> On Saturday, March 1, 2014 3:12:03 PM UTC-5, ccampana wrote:
>
>> *Hi,*
>> *I am not familiar with the CP2K inner workings but if you want to
>> understand the basis of why fitting ESP charges for periodic systems
>> requires extra care I recommend you read the paper below.*
>> *DOI: *10.1021/ct9003405
>> Carlos
>>
>>
>> On Sat, Mar 1, 2014 at 3:02 PM, mbellucci <mbel... at gmail.com> wrote:
>>
>>>
>>> Dear CP2K Users,
>>>
>>> I am trying to calculate the RESP charges for a unit cell of the form I
>>> crystal of paracetamol using periodic boundary conditions using version 2.5
>>> of CP2K.  I have tried many different things but in every calculation, the
>>> RESP charges seem to be unphysical, i.e. the magnitudes of the charges seem
>>> to very large and most have the wrong sign.  The things I have tried in
>>> order to fix this include:
>>>
>>> increasing the cutoff
>>> changing the functional
>>> increasing the size of the basis set
>>> changing the values of the LENGTH and RANGE keywords in the PERIODIC_SYS
>>> section of RESP
>>> changing the SURF_DIRECTION in the PERIODIC_SYS section of RESP
>>> I've also experimented with the keywords WIDTH,
>>> RESTRAIN_HEAVIES_STRENGTH, and RESTRAIN_HEAVIES_TO_ZERO in RESP
>>>
>>> Nothing seems to work for the RESP charges.  However, when I turn off
>>> the periodic boundary conditions the calculations produce RESP charges that
>>> make physical sense.  Also, for calculations with or without periodic
>>> boundary conditions, the DDAP charges make physical sense, but I'm hesitant
>>> to use them in MD simulations since they are less frequently used in MD
>>> simulations in the literature.  If anyone could help identify an error I am
>>> making when calculating these RESP charges, I would greatly appreciate it!
>>>  Also, if anyone could comment on the reliability of DDAP charges in
>>> general, I would appreciate it as well.
>>>
>>> For the calculation, the coordinates of the form I crystal as well as
>>> the dimensions of the unit cell were obtained from the cambridge structural
>>> database.  The input file I'm using, the outputted RESP charges, and the
>>> outputted DDAP charges are the following:
>>>
>>> &GLOBAL
>>>   PROJECT form_1
>>>   RUN_TYPE ENERGY_FORCE
>>>   PRINT_LEVEL MEDIUM
>>>   WALLTIME 86400
>>> &END GLOBAL
>>>
>>> &FORCE_EVAL
>>>   METHOD Quickstep
>>>   &DFT
>>>     BASIS_SET_FILE_NAME EMSL_BASIS_SETS
>>>     POTENTIAL_FILE_NAME POTENTIAL
>>>     CHARGE 0
>>>     MULTIPLICITY 1
>>>      &MGRID
>>>       CUTOFF 300
>>>       REL_CUTOFF 50
>>>     &END MGRID
>>>
>>>     &QS
>>>       METHOD GAPW
>>>       EPS_DEFAULT  1.0E-12
>>>       MAP_CONSISTENT TRUE
>>>       EXTRAPOLATION ASPC
>>>       EXTRAPOLATION_ORDER 3
>>>     &END QS
>>>
>>>     &SCF
>>>       MAX_SCF 500
>>>       SCF_GUESS ATOMIC
>>>       EPS_SCF 1.0E-7
>>>       &OT ON
>>>         MINIMIZER DIIS
>>>         PRECONDITIONER FULL_ALL
>>>         ENERGY_GAP 0.001
>>>       &END OT
>>>
>>>       &OUTER_SCF
>>>          EPS_SCF 1.0E-5
>>>          MAX_SCF 100
>>>       &END OUTER_SCF
>>>     &END SCF
>>>
>>>     &XC
>>>       &XC_FUNCTIONAL PBE
>>>       &END XC_FUNCTIONAL
>>>     &END XC
>>>   &END DFT
>>>
>>>
>>>   &SUBSYS
>>>     &CELL
>>>       ABC 12.93 9.40 7.10
>>>       ALPHA_BETA_GAMMA 90.00 115.90 90.00
>>>       PERIODIC XYZ
>>>     &END CELL
>>>
>>>     &COORD
>>>  C         9.510000        3.334000        5.417000
>>>  C        10.770000        3.348000        4.827000
>>>  C        11.771000        2.497000        5.288000
>>>  C        11.518000        1.636000        6.343000
>>>  C        10.266000        1.639000        6.953000
>>>  C         9.279000        2.483000        6.489000
>>>  C         8.231000        4.763000        3.830000
>>>  C         6.944000        5.542000        3.720000
>>>  H        10.930000        3.957000        4.145000
>>>  H        12.675000        2.557000        4.918000
>>>  H        10.101000        1.062000        7.690000
>>>  H         8.407000        2.482000        6.891000
>>>  H        12.348000        0.517000        7.562000
>>>  H         7.724000        4.239000        5.582000
>>>  H         6.614000        5.480000        2.836000
>>>  H         6.512000        5.574000        4.484000
>>>  H         7.181000        6.589000        3.692000
>>>  N         8.426000        4.170000        5.017000
>>>  O        12.536000        0.800000        6.745000
>>>  O         9.035000        4.678000        2.901000
>>>  C         6.784000        8.034000        0.970000
>>>  C         5.524000        8.048000        1.560000
>>>  C         4.523000        7.197000        1.099000
>>>  C         4.776000        6.336000        0.044000
>>>  C         6.028000        6.339000       -0.567000
>>>  C         7.015000        7.183000       -0.102000
>>>  C         8.063000        9.463000        2.557000
>>>  C         9.350000       10.242000        2.667000
>>>  H         5.364000        8.657000        2.242000
>>>  H         3.618000        7.257000        1.469000
>>>  H         6.193000        5.762000       -1.303000
>>>  H         7.887000        7.182000       -0.505000
>>>  H         3.945000        5.217000       -1.175000
>>>  H         8.570000        8.939000        0.805000
>>>  H         9.680000       10.180000        3.551000
>>>  H         9.782000       10.274000        1.903000
>>>  H         9.113000       11.289000        2.695000
>>>  N         7.867000        8.870000        1.370000
>>>  O         3.758000        5.500000       -0.358000
>>>  O         7.259000        9.378000        3.486000
>>>  C         0.319000        6.066000        0.970000
>>>  C        -0.941000        6.052000        1.560000
>>>  C        -1.942000        6.903000        1.099000
>>>  C        -1.689000        7.764000        0.044000
>>>  C        -0.437000        7.761000       -0.567000
>>>  C         0.550000        6.917000       -0.102000
>>>  C         1.598000        4.637000        2.557000
>>>  C         2.885000        3.858000        2.667000
>>>  H        -1.101000        5.443000        2.242000
>>>  H        -2.847000        6.843000        1.469000
>>>  H        -0.272000        8.338000       -1.303000
>>>  H         1.422000        6.918000       -0.505000
>>>  H        -2.520000        8.883000       -1.175000
>>>  H         2.105000        5.161000        0.805000
>>>  H         3.215000        3.920000        3.551000
>>>  H         3.317000        3.826000        1.903000
>>>  H         2.648000        2.811000        2.695000
>>>  N         1.402000        5.230000        1.370000
>>>  O        -2.707000        8.600000       -0.358000
>>>  O         0.794000        4.722000        3.486000
>>>  C         3.045000        1.366000        5.417000
>>>  C         4.305000        1.352000        4.827000
>>>  C         5.306000        2.203000        5.288000
>>>  C         5.053000        3.064000        6.343000
>>>  C         3.801000        3.061000        6.953000
>>>  C         2.814000        2.217000        6.489000
>>>  C         1.766000       -0.063000        3.830000
>>>  C         0.479000       -0.842000        3.720000
>>>  H         4.465000        0.743000        4.145000
>>>  H         6.210000        2.143000        4.918000
>>>  H         3.636000        3.638000        7.690000
>>>  H         1.942000        2.218000        6.891000
>>>  H         5.883000        4.183000        7.562000
>>>  H         1.259000        0.461000        5.582000
>>>  H         0.149000       -0.780000        2.836000
>>>  H         0.047000       -0.874000        4.484000
>>>  H         0.716000       -1.889000        3.692000
>>>  N         1.961000        0.530000        5.017000
>>>  O         6.071000        3.900000        6.745000
>>>  O         2.570000        0.022000        2.901000
>>>     &END COORD
>>>
>>>
>>>     &KIND H
>>>       BASIS_SET 6-31++Gxx
>>>       POTENTIAL GTH-PBE-q1
>>>     &END KIND
>>>
>>>     &KIND C
>>>       BASIS_SET 6-31++Gxx
>>>       POTENTIAL GTH-PBE-q4
>>>     &END KIND
>>>
>>>     &KIND N
>>>       BASIS_SET 6-31++Gxx
>>>       POTENTIAL GTH-PBE-q5
>>>     &END KIND
>>>
>>>     &KIND O
>>>       BASIS_SET 6-31++Gxx
>>>       POTENTIAL GTH-PBE-q6
>>>     &END KIND
>>>
>>>   &END SUBSYS
>>>
>>>   &PROPERTIES
>>>     &RESP
>>>       &PERIODIC_SYS
>>>         ATOM_LIST 1..80
>>> LENGTH 3.0
>>>  RANGE  3.0 5.0
>>> SURF_DIRECTION Z
>>>       &END PERIODIC_SYS
>>>       &PRINT
>>> &V_RESP_CUBE
>>>  &END V_RESP_CUBE
>>> &RESP_CHARGES_TO_FILE
>>> &END RESP_CHARGES_TO_FILE
>>>  &PROGRAM_RUN_INFO
>>> &END
>>> &COORD_FIT_POINTS
>>> &END
>>>       &END PRINT
>>>
>>>     &END RESP
>>>
>>>     &FIT_CHARGE
>>>     &END FIT_CHARGE
>>>
>>>   &END PROPERTIES
>>>
>>> &END FORCE_EVAL
>>>
>>>
>>>
>>>
>>> RESP charges:
>>>   Type |   Atom   |    Charge
>>>
>>>   RESP       1  C     0.070078
>>>   RESP       2  C     0.903292
>>>   RESP       3  C     1.113722
>>>   RESP       4  C    -0.120125
>>>   RESP       5  C     1.058323
>>>   RESP       6  C     0.655164
>>>   RESP       7  C     0.200902
>>>   RESP       8  C     2.666416
>>>   RESP       9  H    -1.222912
>>>   RESP      10  H    -1.170830
>>>   RESP      11  H    -0.983979
>>>   RESP      12  H    -0.818745
>>>   RESP      13  H    -1.214944
>>>   RESP      14  H    -1.366249
>>>   RESP      15  H    -1.224385
>>>   RESP      16  H    -1.119378
>>>   RESP      17  H    -1.137280
>>>   RESP      18  N     1.259042
>>>   RESP      19  O     1.713353
>>>   RESP      20  O     0.738109
>>>   RESP      21  C     0.041413
>>>   RESP      22  C     0.956097
>>>   RESP      23  C     1.040182
>>>   RESP      24  C    -0.082712
>>>   RESP      25  C     1.051482
>>>   RESP      26  C     0.595410
>>>   RESP      27  C     0.202160
>>>   RESP      28  C     2.662283
>>>   RESP      29  H    -1.166123
>>>   RESP      30  H    -1.126516
>>>   RESP      31  H    -0.984189
>>>   RESP      32  H    -0.800838
>>>   RESP      33  H    -1.188989
>>>   RESP      34  H    -1.401436
>>>   RESP      35  H    -1.215709
>>>   RESP      36  H    -1.113423
>>>   RESP      37  H    -1.128041
>>>   RESP      38  N     1.271056
>>>   RESP      39  O     1.679915
>>>   RESP      40  O     0.705805
>>>   RESP      41  C     0.116651
>>>   RESP      42  C     0.813652
>>>   RESP      43  C     1.108160
>>>   RESP      44  C    -0.087035
>>>   RESP      45  C     1.066794
>>>   RESP      46  C     0.598212
>>>   RESP      47  C     0.201601
>>>   RESP      48  C     2.665972
>>>   RESP      49  H    -1.193708
>>>   RESP      50  H    -1.119339
>>>   RESP      51  H    -0.987625
>>>   RESP      52  H    -0.794927
>>>   RESP      53  H    -1.193920
>>>   RESP      54  H    -1.403616
>>>   RESP      55  H    -1.227170
>>>   RESP      56  H    -1.113105
>>>   RESP      57  H    -1.132964
>>>   RESP      58  N     1.272201
>>>   RESP      59  O     1.669491
>>>   RESP      60  O     0.737908
>>>   RESP      61  C     0.017005
>>>   RESP      62  C     0.961044
>>>   RESP      63  C     1.064429
>>>   RESP      64  C    -0.116028
>>>   RESP      65  C     1.044203
>>>   RESP      66  C     0.665757
>>>   RESP      67  C     0.203199
>>>   RESP      68  C     2.660164
>>>   RESP      69  H    -1.159143
>>>   RESP      70  H    -1.166104
>>>   RESP      71  H    -0.983609
>>>   RESP      72  H    -0.830205
>>>   RESP      73  H    -1.208912
>>>   RESP      74  H    -1.380887
>>>   RESP      75  H    -1.210223
>>>   RESP      76  H    -1.114933
>>>   RESP      77  H    -1.129467
>>>   RESP      78  N     1.264612
>>>   RESP      79  O     1.718065
>>>   RESP      80  O     0.706396
>>>   Total               0.000000
>>>
>>>
>>>  DDAP FULL DENSITY charges:
>>>   Atom     |    Charge
>>>
>>>      1  C     0.164768
>>>      2  C     0.038789
>>>      3  C    -0.067304
>>>      4  C     0.359095
>>>      5  C    -0.273509
>>>      6  C    -0.132861
>>>      7  C     0.453357
>>>      8  C    -0.073176
>>>      9  H    -0.008341
>>>     10  H    -0.007149
>>>     11  H     0.160840
>>>     12  H     0.127025
>>>     13  H     0.128967
>>>     14  H     0.094082
>>>     15  H    -0.056650
>>>     16  H    -0.027392
>>>     17  H    -0.004180
>>>     18  N    -0.249484
>>>     19  O    -0.299466
>>>     20  O    -0.327283
>>>     21  C     0.164803
>>>     22  C     0.039171
>>>     23  C    -0.067954
>>>     24  C     0.359126
>>>     25  C    -0.273851
>>>     26  C    -0.132660
>>>     27  C     0.453316
>>>     28  C    -0.072910
>>>     29  H    -0.008512
>>>     30  H    -0.006834
>>>     31  H     0.161121
>>>     32  H     0.126815
>>>     33  H     0.128910
>>>     34  H     0.094007
>>>     35  H    -0.056723
>>>     36  H    -0.027522
>>>     37  H    -0.004288
>>>     38  N    -0.249623
>>>     39  O    -0.299372
>>>     40  O    -0.327146
>>>     41  C     0.164786
>>>     42  C     0.039184
>>>     43  C    -0.067967
>>>     44  C     0.359125
>>>     45  C    -0.273855
>>>     46  C    -0.132651
>>>     47  C     0.453282
>>>     48  C    -0.072882
>>>     49  H    -0.008520
>>>     50  H    -0.006829
>>>     51  H     0.161118
>>>     52  H     0.126809
>>>     53  H     0.128911
>>>     54  H     0.094000
>>>     55  H    -0.056734
>>>     56  H    -0.027529
>>>     57  H    -0.004294
>>>     58  N    -0.249597
>>>     59  O    -0.299364
>>>     60  O    -0.327128
>>>     61  C     0.164787
>>>     62  C     0.038773
>>>     63  C    -0.067297
>>>     64  C     0.359102
>>>     65  C    -0.273505
>>>     66  C    -0.132867
>>>     67  C     0.453392
>>>     68  C    -0.073203
>>>     69  H    -0.008330
>>>     70  H    -0.007154
>>>     71  H     0.160838
>>>     72  H     0.127032
>>>     73  H     0.128964
>>>     74  H     0.094090
>>>     75  H    -0.056640
>>>     76  H    -0.027383
>>>     77  H    -0.004176
>>>     78  N    -0.249513
>>>     79  O    -0.299471
>>>     80  O    -0.327306
>>>   Total       0.000000
>>>
>>>
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