P. J. Knowles and H.-J. Werner (1984).

Bibliography:

H.-J. Werner and P. J. Knowles, J. Chem. Phys. 82, 5053 (1985).

P. J. Knowles and H.-J. Werner, Chem. Phys. Lett. 115, 259 (1985).

All publications resulting from use of this program must acknowledge the above. See also:

H.-J. Werner and W. Meyer, J. Chem. Phys. 73, 2342 (1980).

H.-J. Werner and W. Meyer, J. Chem. Phys. 74, 5794 (1981).

H.-J. Werner, Adv. Chem. Phys. LXIX, 1 (1987).

This program allows one to perform CASSCF as well as general MCSCF calculations. For CASSCF calculations, one can optionally use Slater determinants or CSFs as a -electron basis. In most cases, the use of Slater determinants is more efficient. General MCSCF calculations must use CSFs as a basis.

A quite sophisticated optimization method is used. The algorithm is second-order in the
orbital and CI coefficient changes and is therefore quadratically convergent. Since
important higher order terms in the independent orbital parameters are included, almost
cubic convergence is often observed. For simple cases, convergence is usually achieved in
2-3 iterations. However, convergence problems can still occur in certain applications, and
usually indicate that the active space is not adequately chosen. For instance, if two
weakly occupied orbitals are of similar importance to the energy, but only one of them is
included in the active set, the program might alternate between them. In such cases either
reduction or enlargement of the active orbital space can solve the problem. In other cases
difficulties can occur if two electronic states in the same symmetry are almost or exactly
degenerate, since then the program can switch from one state to the other. This might
happen near avoided crossings or near an asymptote. Problems of this sort can be avoided by
optimizing the energy average of the particular states. It is also possible to force
convergence to specific states by choosing a subset of configurations as primary space
(`PSPACE`). The hamiltonian is constructed and diagonalized explicitly in this space; the
coefficients of the remaining configurations are optimized iteratively using the P-space
wavefunction as zeroth order approximation. For linear molecules, another possibility is to
use the `LQUANT` option, which makes it possible to force convergence to states with
definite quantum number, i.e., , , , etc. states.

- 19.1 Structure of the input
- 19.2 Defining the orbital subspaces
- 19.3 Defining the optimized states
- 19.4 Defining the configuration space
- 19.5 Restoring and saving the orbitals and CI vectors
- 19.6 Selecting the optimization methods
- 19.7 Calculating expectation values
- 19.8 Miscellaneous options
- 19.9 Coupled-perturbed MCSCF
- 19.10 Optimizing valence bond wavefunctions
- 19.11 Total Position-Spread tensor (TPS)
- 19.12 Hints and strategies
- 19.13 Examples

manual quickstart instguide update basis

molpro@molpro.net 2018-01-22