Analytic Gradients for Restricted Active Space Second-order Perturbation Theory (RASPT2)

The computational cost of analytic derivatives in multireference perturbation theory is strongly affected by the size of the active space employed in the reference self-consistent field calculation. To overcome previous limits on active space size, the analytic gradients of single-state restricted active space second-order perturbation theory (RASPT2) and its complete active space variant (CASPT2) have been developed and implemented in a local version of OpenMolcas. Similar to previous implementations of CASPT2, the RASPT2 implementation employs the Lagrangian or Z-vector method.
The numerical results show that restricted active spaces with up to 20 electrons in 20 orbitals can now be employed for geometry optimizations.