[CP2K-user] [CP2K:17462] Re: orthogonal lattice gives same exact energy as strained--PBC being applied?

Ronald Cohen recohen3 at gmail.com
Thu Aug 11 11:53:26 UTC 2022


BTW The problems I have been having with NMR seem to be related to the 
basis sets. I was using the pcSseg basis sets, which seems to work fine for 
molecules, but was getting huge unphysical chemical shifts for periodic 
crystals (*****).  When I switched to EMSL 6-31G** I am getting reasonable 
numbers.

Ron


On Wednesday, August 10, 2022 at 11:22:50 AM UTC-4 Ronald Cohen wrote:

> Yes, but I think it changes too little? I am still testing. Thank you! Ron
>
> --
> Ron Cohen
> reco... at gmail.com
> On Aug 10, 2022, 11:06 AM -0400, Matt Watkins <mattwa... at gmail.com>, 
> wrote:
>
> Hi, 
> the energy does change but in the SCF loop it is given with reduced number 
> of figures
>
> (base) mattw at DESKTOP:~/NMR/nmr1$ grep 'Total energy:' *out
>   Total energy:                                           
>  -23467.23741478025477
> (base) mattw at DESKTOP:~/NMR/nmr1$ cd madeorthogonal/
> (base) mattw at DESKTOP:~/NMR/nmr1/madeorthogonal$ grep 'Total energy:' *out
>   Total energy:                                           
>  -23467.23741478026932
>
> You could test the orthogonal / nonorthogonal hypothesis on a smaller 
> system! I suspect you are correct that there is an assumption in one of the 
> operators that the box is orthogonal.
> Matt
>
> On Wednesday, 10 August 2022 at 14:23:05 UTC+1 reco... at gmail.com wrote:
>
>> This is too weird. I just ran across the strangest thing. I am trying to 
>> figure out why nmr is not working--I get things like at the bottom (see 
>> NMR). So I wanted to see if the problem was that the cell was not 
>> orthogonal, so I strained the cell to make it orthogonal without changing 
>> the positions of the atoms in the cell. It gave exactly the same energy as 
>> if periodic boundary conditions (PBC) are not being used!!  
>>
>> CP2K| version string:                 CP2K version 2022.1 (Development 
>> Version)
>>  CP2K| source code revision number:                                 
>>  git:2de0518
>>  CP2K| cp2kflags: omp libint fftw3 libxc pexsi elpa parallel mpi3 
>> scalapack cosm
>>  CP2K|            a xsmm max_contr=4 plumed2 spglib mkl sirius libvori 
>> libbqb
>>
>>
>> *Unmodified:*
>> CELL_TOP| Volume [angstrom^3]:                                     
>>  1195.278954
>>  CELL_TOP| Vector a [angstrom    12.264     0.000     0.000   |a| =   
>>  12.263717
>>  CELL_TOP| Vector b [angstrom    -0.012    12.207     0.000   |b| =   
>>  12.206735
>>  CELL_TOP| Vector c [angstrom     0.010    -0.018     7.985   |c| =     
>> 7.984530
>>  CELL_TOP| Angle (b,c), alpha [degree]:                               
>>  90.131000
>>  CELL_TOP| Angle (a,c), beta  [degree]:                               
>>  89.925000
>>  CELL_TOP| Angle (a,b), gamma [degree]:                               
>>  90.057000
>>  CELL_TOP| Numerically orthorhombic:                                     
>>      NO
>>  
>>    43 OT DIIS     0.15E+00   69.7     4.9884E-12    *-23467.2374147803* 
>>  1.09E-11
>>
>>   *** SCF run converged in    43 steps ***
>>
>>
>>   Electronic density on regular grids:      -1079.0687219005      530.
>> 9312780995 <(931)%20278-0995>
>>   Core density on regular grids:             1610.0000000000       
>>  0.0000000000
>>   Hard and soft densities (Lebedev):        -8290.7114735740    -7759.
>> 7802260448 <(780)%20226-0448>
>>   Total Rho_soft + Rho1_hard - Rho1_soft    -1609.9999694297
>>   Total charge density (r-space):               0.0000305703
>>   Total Rho_soft + Rho0_soft (g-space):         0.0000329359
>>
>>   Overlap energy of the core charge distribution:               
>> 0.00000104541775
>>   Self energy of the core charge distribution:             
>> -14539.93646441583769
>>   Core Hamiltonian energy:                                 
>>  -9218.15471874043033
>>   Hartree energy:                                           
>>  3922.43227166635324
>>   Exchange-correlation energy:                               
>> -646.66529311302361
>>
>>   GAPW| Exc from hard and soft atomic rho1:                 
>> -1396.13990389988862
>>   GAPW| local Eh = 1 center integrals:                     
>>  -1588.77330732284054
>>
>>   Total energy:                                           
>>  -23467.23741478025477
>>
>>   outer SCF iter =    1 RMS gradient =   0.50E-11 energy =     
>> -23467.2374147803
>>
>>
>> *Made orthogonal*
>> CELL_TOP| Volume [angstrom^3]:                                     
>>  1200.135541
>>  CELL_TOP| Vector a [angstrom    12.260     0.000     0.000   |a| =   
>>  12.260000
>>  CELL_TOP| Vector b [angstrom     0.000    12.260     0.000   |b| =   
>>  12.260000
>>  CELL_TOP| Vector c [angstrom     0.000     0.000     7.985   |c| =     
>> 7.984530
>>  CELL_TOP| Angle (b,c), alpha [degree]:                               
>>  90.000000
>>  CELL_TOP| Angle (a,c), beta  [degree]:                               
>>  90.000000
>>  CELL_TOP| Angle (a,b), gamma [degree]:                               
>>  90.000000
>>  CELL_TOP| Numerically orthorhombic:                                     
>>     YES
>>
>> *Note even volume is different*
>>
>>   44 OT DIIS     0.15E+00   69.8     4.5499E-12   * -23467.2374147803* 
>> -3.27E-11
>> EXACT SAME AS ABOVE!
>>   *** SCF run converged in    44 steps ***
>>
>>
>>   Electronic density on regular grids:      -1079.0687219005      530.
>> 9312780995 <(931)%20278-0995>
>>   Core density on regular grids:             1610.0000000000       
>>  0.0000000000
>>   Hard and soft densities (Lebedev):        -8290.7115342968    -7759.
>> 7802867676 <(780)%20286-7676>
>>   Total Rho_soft + Rho1_hard - Rho1_soft    -1609.9999694297
>>   Total charge density (r-space):               0.0000305703
>>   Total Rho_soft + Rho0_soft (g-space):         0.0000329359
>>
>>   Overlap energy of the core charge distribution:               
>> 0.00000104541775
>>   Self energy of the core charge distribution:             
>> -14539.93646441583769
>>   Core Hamiltonian energy:                                 
>>  -9218.15471874045579
>>   Hartree energy:                                           
>>  3922.43227166633824
>>   Exchange-correlation energy:                               
>> -646.66529311301952
>>
>>   GAPW| Exc from hard and soft atomic rho1:                 
>> -1396.13990389988476
>>   GAPW| local Eh = 1 center integrals:                     
>>  -1588.77330732282644
>>
>>   Total energy:                                           
>>  -23467.23741478026932
>>
>>   outer SCF iter =    1 RMS gradient =   0.45E-11 energy =     
>> -23467.2374147803
>>   outer SCF loop converged in   1 iterations or   44 steps
>>
>>
>> Note both show
>> POISSON| Solver                                                       
>>  PERIODIC
>>  POISSON| Periodicity                                                     
>>    XYZ
>> in input .INC FILES
>>        PERIODIC  XYZ FOR BOTH
>> seems cell periodicity is not output?
>>
>> Any help appreciated! Files attached.
>> ----NMR
>>
>> Shielding atom at atomic positions. # tensors printed 165
>>
>> 1O O 2.390434 2.226322 0.031347
>>
>> SIGMA from SOFT J
>>
>> XX = ********** XY = ********** XZ = **********
>>
>> YX = ********** YY = ********** YZ = **********
>>
>> ZX = ********** ZY = ********** ZZ = **********
>>
>> SIGMA from LOCAL J
>>
>> XX = -5315.3694 XY = ********** XZ = **********
>>
>> YX = 98.5820 YY = ********** YZ = **********
>>
>> ZX = 1884.0679 ZY = ********** ZZ = **********
>>
>> SIGMA TOTAL
>>
>> XX = ********** XY = ********** XZ = **********
>>
>> YX = ********** YY = ********** YZ = **********
>>
>> ZX = ********** ZY = ********** ZZ = **********
>>
>> ISOTROPY = ************ ANISOTROPY = ************
>>
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