21.1 Introduction

Multireference perturbation calculations are performed by the MRCI program as a special case. For RS2 (CASPT2,RASPT2) only matrix elements over a one-electron operator need to be computed, and therefore the computational effort is much smaller than for a corresponding MRCI. For RS3 (CASPT3) the energy expectation value for the first-order wavefunction must be computed and the computational effort is about the same as for one MRCI iteration. The RS2 and RS3 programs use the same configuration spaces as the MRCI, i.e., only the doubly external configurations are internally contracted.

A new version of the program has been implemented in which also subspaces of the singly external and internal configuration spaces are internally contracted (see reference given above). This program, which is called using the keyword RS2C, is more efficient than RS2, in particular for large molecules with many closed-shell (inactive) orbitals. It is recommended to use this program for normal applications of second-order multireference perturbation theory (CASPT2, RASPT2). Note that it gives slightly different results than RS2 due to the different contraction scheme. It should also be noted that neither RS2 or RS2C are identical with the CASPT2 of Roos et al. [J. Chem. Phys. 96, 1218 (1992)], since certain configuration subspaces are left uncontracted. However, the differences are normally very small. The last point that should be mentioned is that the calculation of CASPT2/RASPT2 density matrices (and therefore molecular properties) is presently possible only with the RS2 command and not with RS2C.

The results of multireference perturbation theory may be sensitive to the choice of the zeroth-order Hamiltonian. This dependence is more pronounced in second-order than in third-order. Several options are available, which will be described in the following sections. It may also happen that $(\hat H^{(0)} - E^{(0)})$ in the basis of the configuration state functions becomes (nearly) singular. This is known as "intruder state problem" and can cause convergence problems or lead to a blow-up of the wavefunction. Often, such problems can be eliminated by including more orbitals into the reference wavefunction, but of course this leads to an increase of the CPU time. The use of modified Fock operators (see below) or level shifts, as proposed by Roos and Andersson [Chem. Phys. Lett. 245, 215 (1995)] may also be helpful. Presently, only "real" level shifts have been implemented.

With no further input cards, the wavefunction definition (core, closed, and active orbital spaces, symmetry) corresponds to the one used in the most recently done SCF or MCSCF calculation. By default, a CASSCF reference space is generated. Other choices can be made using the OCC, CORE, CLOSED, WF, SELECT, CON, and RESTRICT cards, as described for the CI program. The orbitals are taken from the corresponding SCF or MCSCF calculation unless an ORBITAL directive is given.

For a CASPT2 calculation, the zeroth-order Hamiltonian can be brought to a block-diagonal form when (pseudo)canonical orbitals are used. This leads to fastest convergence. It is therefore recommended that in the preceding MULTI calculation the orbitals are saved using the CANONICAL directive (note that the default is NATORB).

Most options for MRCI calculations (like STATE, REFSTATE etc.) apply also for RS2(C) and RS3 and are not described here again. Some additional options which specific for CASPT2/3 and are described below.

molpro@molpro.net 2019-06-16