21.8 Coupling MRCI and MRPT2: The CIPT2 method

P. Celani, H. Stoll, H.-J. Werner and P. J. Knowles, Mol. Phys. 102, 2369 (2004).

For particularly difficult cases with strong intruder problems, or in which second-order perturbation theory fails to predict reliable results, a new method that couples MRCI and CASPT2 has been developed. This variant is invoked using the CIPT2 directive:


In this case all excitations solely from active orbitals are treated by MRCI, while the remaining excitations involving inactive (closed-shell) orbitals are treated by second-order perturbation theory. Both methods are coupled by minimizing an appropriate energy functional. Of course, this method is much more expensive that MRPT2. The cost is comparable to the cost for an MRCI without correlating the inactive orbitals.

molpro@molpro.net 2020-04-18