8.5 Pseudopotentials and Electron Correlation

The pseudopotential package is integrated with the electron correlation package and it is therefore possible to apply any of Q-Chem’s post-Hartree-Fock methods to systems in which some of the atoms may bear pseudopotentials. Of course, the correlation energy contribution arising from core electrons that have been replaced by an ECP is not included. In this sense, correlation energies with ECPs are comparable to correlation energies from frozen core calculations. However, the use of ECPs effectively removes both core electrons and the corresponding virtual (unoccupied) orbitals.

8.5.1 Example

Example 8.186 Optimization of the structure of Se $_{8}$ using HF/LANL2DZ, followed by a single-point energy calculation at the MP2/LANL2DZ level.

$molecule
   0  1
   x1
   x2   x1  xx
   Se1  x1  sx  x2  90.
   Se2  x1  sx  x2  90.  Se1  90.
   Se3  x1  sx  x2  90.  Se2  90.
   Se4  x1  sx  x2  90.  se3  90.
   Se5  x2  sx  x1  90.  Se1  45.
   Se6  x2  sx  x1  90.  Se5  90.
   Se7  x2  sx  x1  90.  Se6  90.
   Se8  x2  sx  x1  90.  Se7  90.

   xx = 1.2
   sx = 2.8
$end

$rem
   JOBTYP     opt 
   METHOD     hf      
   ECP        lanl2dz 
$end

@@@

$molecule
   read
$end

$rem
   JOBTYP        sp        Single-point energy
   METHOD        mp2       MP2 correlation energy
   ECP           lanl2dz   Hay-Wadt ECP and basis
   SCF_GUESS     read      Read in the MOs
$end