Often, no further input is necessary. By default, the number of electrons is equal to the nuclear charge, the wavefunction is assumed to be totally symmetric (symmetry 1), and the spin multiplicity is 1 (singlet) for an even number of electrons and 2 (doublet) otherwise. The Aufbau principle is used to determine the occupation numbers in each symmetry. Normally, this works well in closed-shell cases, but sometimes wrong occupations are obtained or the wavefunction alternates between different orbital spaces. In such cases, the OCC directive must be used to force convergence to the desired state. The default behaviour can be modified either by options on the command line, or by directives.
In open-shell cases, we recommend to use the WF, OCC, CLOSED, or OPEN cards to define the wavefunction uniquely. Other commands frequently used are START and ORBITAL (or SAVE) to modify the default records for starting and optimized orbitals, respectively. The SHIFT option or directive allows to modify the level shift in the RHF program, and EXPEC to calculate expectation values of one-electron operators (see section 6.13).
Density fitting can be used for closed and open-shell spin-restricted HF and is involked by a prefix DF- (DF-HF or DF-RHF, see section 11). For UHF, only Coulomb fitting is possible (CF-UHF). Density fitting very much speeds up calculations for large molecules. The greatest savings are seen for large basis sets with high angular momentum functions. For details see R. Polly, H.-J. Werner, F. R. Manby, and Peter J. Knowles, Fast Hartree-Fock theory using local density fitting approximations, Mol. Phys. 102, 2311 (2004). All publications resulting from DF-HF or DF-KS calculations should cite this work.
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