By Alan Hinchliffe; et al
Content material: Vol. 1 -- Vol. 2. A assessment of the literature released among June 1999 and will 2001 -- Vol. three. A assessment of the literature released among June 2001 and will 2003 -- Vol. four. A overview of modern literature released among June 2003 and will 2005
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Extra info for Chemical Modelling Applications and Theory, Vol. 3
2 Variational Computations. - Variational computations are based upon the calculation of matrix elements between functions of all the internal coordinates. 58), which is the direct product form for normal coordinates constructed from a basis of single variable functions. A collection of such many variable functions is called an internal coordinate basis. The single variable functions can be thought of as a bit like molecular orbitals in electronic structure calculations. The symmetry of the functional forms reflects the symmetry of the potential and permutational symmetry in relation to the requirements of the Pauli principle is not usually considered.
26) In the above, the elements of Qi and of aiare dependent on internal variables only, while the elements of C and of D are functions of the Eulerian angles only. It is usually possible to express the internal coordinates of a problem as explicit functions of the scalar products of the translationally invariant coordinates. 26). 25) involves great ingenuity and much good-luck and sometimes it is a labour undertaken without success. There are a couple of tricks which are sometimes used in this context.
The choice made in the Eckart approach ensures that the coupling of the angular to the internal motions is minimised and thus the internal coordinate basis may be chosen to be largely independent of J and k. However, with the standard choice of internal coordinate basis, it is not easy to deal with large amplitude motions. The placing of the molecule in the x - z plane allows the elements of the effective vibration-rotation operator to be chosen real and thus simplifies their calculation. If bond-length and bond-angle internal coordinates are chosen, the single variable function of bond-angle coordinate must be chosen to depend on k to be effective, yielding internal coordinate basis functions which are coupled to the rotational motion.