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Finding Minima

To optimise a molecular geometry, use the keyword OPTIMISE (or OPTIMIZE, the two spellings are equivalent!). Optimisations are possible if analytic gradients are available - a list is given in the preceding section. For an example consider this dataset for the hydrogen fluoride dimer.
TITLE
HF-HF  OPT
SYMMETRY
CS
END
BASIS 631G**
VARIABLES
RFF    2.75 A
RFH1   0.912 A
RFH2   0.912 A
THETA1  5.0 D
THETA2  -110.0  D
END
ATOMS
F1 9 0 0 0
F2 9 0 0 RFF
H1 1 POL RFH1 THETA1 0
H2 1 PTC F2 F1 H1 RFH2 THETA2
END
OPTIMISE
START
FINISH
This example sets up the initial geometry in internal coordinates, the the initial values of the parameters declared as variables. The OPTIMISE keyword causes a geometry optimisation to be carried out resulting in an optimised geometry after several steps.

The gradients on each step are displayed in the following form - the gradient is in internal coordinates because the geometry was specified in those coordinates.

    Parameter                 value                 gradient
      name          (bohr or        (angstrom
                     radian)        or degree)
      RFF           5.15702682      2.72898127      0.00009552
      RFH1          1.70967460      0.90472090      0.00000851
      RFH2          1.70772980      0.90369176     -0.00000904
      THETA1        0.24962520     14.30247061      0.00000922
      THETA2       -1.77558739   -101.73366372      0.00002072
This is actually the final set of parameters corresponding to the minimum. The final geometry is also given in cartesian coordinates. If the initial geometry had been given in cartesian coordinates then the gradient on each step would also be printed in cartesians, in the format described in the first section in this chapter.

At the end of the optimisation, various properties of the molecule are given - charge densities, atomic populations, dipole and quadrupole moments, the electric fields at the nuclei and the moments of inertia and rotational constants. These are generated automatically and correspond to a call of the PROPERTY directive (see section 6.1).

The above example is for closed-shell SCF, however other types of wavefunction are just as simple - all one has to do is include those directives which specify the type of energy calculation ie closed or open-shell SCF, and whether correlation is included. For example, an MP2 optimisation simply requires the addition of the keyword MP2 to the above dataset.


next  next up previous
Contents: Table of Contents  Next: Constants, Variables and Partial Optimisations Up: Chapter 4 Previous: Calculating one energy gradient