Basis set superposition error¶

The basis set superposition error (BSSE, also known as counterpoise correction) can be estimated by performing subsystem calculations using ghost atoms which carry basis sets of the full system.

This tutorial describes how to use ghost atoms in DIRAC and how to avoid certain pitfalls when working with ghost centers.

Treating BSSE in xyz-files¶

The xyz-reader offers a simple way for dealing with counterpoise procedure. Let us have a look at this example. The Be2.xyz molecule input file labels the second Berylium atom as ‘ghost’ (what means zero charge)

Beryllium dimer
Be   0.0 0.0 0.0
BeGh 0.0 0.0 4.0

The corresponding Dirac input file has to contain the reference to the ghost nucleus with two numbers. The first specifies the atom’s nuclear charge that is used in the calculation (here it is zero), and the second one is the proton number used for searching in basis set files:

**DIRAC
.TITLE
 Be dimer counterpoise correction
.WAVE FUNCTION
**WAVE FUNCTION
.SCF
*SCF
.CLOSED SHELL
 4
.EVCCNV
2.0d-07 2.0d-07
**MOLECULE
*CENTERS
# 2 numbers - nuclear charge for ghost atom and the proton number
.NUCLEUS
BeGh 0.0 4.0
*BASIS
.DEFAULT
cc-pVDZ
**END OF

For more about specifying xyz-files see the How to specify the molecule and basis set using xyz files part of the manual.

Using basis set file in mol-files¶

If you are using the mol-file input with reading of basis set(s) from the file(s), you can use this simple scheme:

INTGRL
 Ne2   neon dimer
 Using aug-cc-pVQZ-basis
C   2    2  X  Y
     0.0     1
Ne  0.0 0.0  -2.55
LARGE BASIS Q=10.0  aug-cc-pVQZ
    10.0      1
Ne2  0.0 0.0   2.55
LARGE BASIS aug-cc-pVQZ
FINISH

The first neon atom is considered as the ‘ghost’ atom with the charge of 0.0 in the mol-file, but also with the “Q=10.0” parameter before the basis set file name (aug-cc-pVQZ). The “Q=...” value represents the real charge of that atom so that the program can find it in user’s specified basis set file.

Explicit giving of ghost atom basis set¶

Last (and least comfortable) way is to type the ghost atom basis set explicitly. This is when there is no basis set file at disposal, and the user has to write basis set exponents (and contraction coefficients) directly into the mol-file.

As to the replacement of a real atom by its ghost atom, it is sufficient to replace the atom’s charge by zero charge. It is recommended to also change the name of the atom.

For instance, this input for a ghost atom with a contracted oxygen aug-cc-pVDZ basis could be given by the following molecule (.mol) file:

        0.    1
Gh      .0000000000        0.0000000000        -.2249058930
LARGE EXPLICIT  3    1    1    1
# s functions
f  10    4
  11720.0000000  0.00071000 -0.00016000  0.00000000  0.00000000
   1759.0000000  0.00547000 -0.00126300  0.00000000  0.00000000
    400.8000000  0.02783700 -0.00626700  0.00000000  0.00000000
    113.7000000  0.10480000 -0.02571600  0.00000000  0.00000000
     37.0300000  0.28306200 -0.07092400  0.00000000  0.00000000
     13.2700000  0.44871900 -0.16541100  0.00000000  0.00000000
      5.0250000  0.27095200 -0.11695500  0.00000000  0.00000000
      1.0130000  0.01545800  0.55736800  0.00000000  0.00000000
      0.3023000 -0.00258500  0.57275900  1.00000000  0.00000000
      0.0789600  0.00000000  0.00000000  0.00000000  1.00000000
# p functions
f   5    3
     17.7000000  0.04301800  0.00000000  0.00000000
      3.8540000  0.22891300  0.00000000  0.00000000
      1.0460000  0.50872800  0.00000000  0.00000000
      0.2753000  0.46053100  1.00000000  0.00000000
      0.0685600  0.00000000  0.00000000  1.00000000
# d functions
f   2    2
      1.1850000  1.00000000  0.00000000
      0.3320000  0.00000000  1.00000000

For detailed know-how about mol files see How to specify the molecule and basis set using the traditional mol files.

DFT grid¶

When you replace an atom by a ghost atom the DFT grid will change. In order to use the same grid for both the full system and the subsystem with ghost atoms, you can export the DFT grid of the full system by copying the file “numerical_grid” from the scratch directory, and import this grid back into the calculation with ghost atoms:

**GRID
.IMPORT
numerical_grid

Make sure to copy the grid file from/to the working directory by using:

pam ... --get=numerical_grid ...

and:

pam ... --copy=numerical_grid ...

Symmetry recognition¶

If you leave the symmetry text in the molecule specification blank, DIRAC will try to evaluate the symmetry of the system automatically. Note that the symmetry recognition uses the atom types and coordinates but not the respective basis sets. This means that if you use ghost atoms with different basis sets, you should give the symmetry explicitly or check the symmetry recognized by DIRAC.

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