Many users will find that the library of built-in ECPs is adequate for their needs. However, if you need to use an ECP that is not built into Q-Chem, you can enter it in much the same way as you can enter a user-defined orbital basis set; see Chapter 8.
To apply a user-defined ECP, you must set the ECP and BASIS keywords in $rem to GEN. You then add a $ecp block that defines your ECP, element by element, and a $basis block that defines your orbital basis set, separating elements by asterisks.
The syntax within the $basis block is described in Chapter 8. The syntax for each record within the $ecp block is as follows:.
For each atom that will bear an ECP:
Chemical symbol for the atom
ECP name; the value for the ECP; number of core electrons removed
For each ECP component (in the order unprojected, , , …, ):
The component name
The number of Gaussians in the component
For each Gaussian in the component
The power of ; the exponent ; the contraction coefficient
A sequence of four asterisks (i.e., ****)
Note: 1. All of the information in the $ecp block is case-insensitive. 2. The power of (which includes the Jacobian factor) must be 0, 1, or 2. 3. If an or term is included you must include the rem keyword “ECP_FIT = TRUE”.
$molecule 0 1 Al H1 Al r H2 Al r H1 120.0 H3 Al r H1 120.0 H2 180.0 r = 1.6 $end $rem JOBTYPE opt Geometry optimization METHOD hf Hartree-Fock theory ECP gen User-defined ECP BASIS gen User-defined basis ECP_FIT true $end $ecp Al Stevens_ECP 2 10 d potential 1 1 1.95559 -3.03055 s-d potential 2 0 7.78858 6.04650 2 1.99025 18.87509 p-d potential 2 0 2.83146 3.29465 2 1.38479 6.87029 **** $end $basis Al SP 3 1.00 0.90110 -0.30377 -0.07929 0.44950 0.13382 0.16540 0.14050 0.76037 0.53015 SP 1 1.00 0.04874 0.32232 0.47724 **** H 3-21G **** $end