Improved SCF algorithms for high-spin open-shell systems

For open-shell systems, RHF and RKS now use a two-step diagonalization process by default: Here the beta orbitals are found by a second diagonalization in the subspace of occupied alpha orbitals. This process usually leads to more stable convergence in difficult cases, compared to the standard diagonalization of a single open-shell Fock matrix (the latter behavior is recovered by {rhf,algo=0}). An additional section with suggestions for dealing with difficult cases has been added to be manual under “The SCF program”. Additionally, various limitations of the SCF program have been lifted. In particular, {rhf; maxit,1} now always works, and just calculates a Fock matrix and energy from the input orbitals, without updating said orbitals.



molpro@molpro.net 2018-09-21