CamCASP/Programming/0

CamCASP => Programming => Status

ENERGY-SCAN

What's working:

• REDO_DF_ON_ROTATION = .TRUE.
  • E1elst, E1exch, E2ind(UC),E2exind(UC),E2exdisp(UC),E2disp(UC)
• REDO_DF_ON_ROTATION = .FALSE.
  • ???

What's not working and why:

• REDO_DF_ON_ROTATION = .TRUE.
  • E2ind & E2disp: The DF-FDDS is created correctly for the first dimer configuration, but as it is not updated, it is incorrect for all subsequent configurations.
  • E2exind & E2exdisp: Since these are obtained by scaling E2exind(UC) & E2exdisp(UC) using E2ind & E2disp (and their UC counterparts), these are wrong too.

Cartesian versus Spherical auxiliary basis sets

What are the errors introduced when we use spherical GTOs in the auxiliary basis?

Water dimer

Sadlej/MC PBE0/AC

Units: kJ/mol

Geometries used:

     Rx      Ry      Rz      alpha   Nx      Ny      Nz       
    1   7.5489   0.0000   0.0000 180.0000   1.0000   0.0000   0.0000 
    2   6.5478   0.0000   0.0000 180.0000   1.0000   0.0000   0.0000 

Since the rotation stays the same, the Cartesian scan which uses REDO_DF_ON_ROTATION=.TRUE. should get all energies correct.

Energies --------Geom 1---------------  ------------Geom2-------------
         reference       JK-tzvpp       reference       JK-tzvpp
                   Spherical Cartesian             Spherical Cartesian
----------------------------------------------------------------------
REDO-DF               F         T                      F         T
----------------------------------------------------------------------
E1elst              -3.527    -3.736               -6.718    -6.897
E1exch               0.129     0.137                1.624     1.718
E2ind              -37.08     -0.181              -97.861    -0.556
E2exind              0.101     0.001                3.616     0.026
E2disp              -1.263    -0.919               -3.384    -2.351
E2exdisp             0.003     0.007                0.030     0.054
======================================================================

Are the JK-tzvpp Aux bases any good?

• <math>\pi</math>-systems?
• H-bonded systems?

CamCASP and truncated MO space

When molecules are too long and/or basis sets are too diffuse, DALTON will often need to truncate the MO space to enable the SCF cycle to converge. So the effective number of MOs will be less than the size of the basis used. Since CamCASP assumes these two are equal (though it doesn't need to), this results in errors.

Where do changes need to be made to fix this?

• Reading in MOs.
• Constructing the density-matrix.
• Rotating MOs.
• DF
• Transformation code.