GF Method - Normal Coordinates in Terms of Cartesian Displacement Coordinates

Normal Coordinates in Terms of Cartesian Displacement Coordinates

Often the normal coordinates are expressed as linear combinations of Cartesian displacement coordinates. Let RA be the position vector of nucleus A and RA0 the corresponding equilibrium position. Then is by definition the Cartesian displacement coordinate of nucleus A. Wilson's linearizing of the internal curvilinear coordinates qt expresses the coordinate St in terms of the displacement coordinates

S_t =\sum_{A=1}^N \sum_{i=1}^3 s^t_{Ai} \, d_{Ai}= \sum_{A=1}^N \mathbf{s}^t_{A} \cdot \mathbf{d}_{A}, \quad \mathrm{for}\quad t = 1,\ldots,3N-6,

where sAt is known as a Wilson s-vector. If we put the into a 3N-6 x 3N matrix B, this equation becomes in matrix language

The actual form of the matrix elements of B can be fairly complicated. Especially for a torsion angle, which involves 4 atoms, it requires tedious vector algebra to derive the corresponding values of the . See for more details on this method, known as the Wilson s-vector method, the book by Wilson et al., or molecular vibration. Now,

\mathbf{Q} = \mathbf{L}^{-1} \mathbf{s} = \mathbf{L}^{-1} \mathbf{B} \mathbf{d} \equiv \mathbf{D} \mathbf{d}.

In summation language:

Q_k = \sum_{A=1}^N \sum_{i=1}^3 D^k_{Ai}\, d_{Ai} \quad \mathrm{for}\quad k=1,\ldots, 3N-6.

Here D is a 3N-6 x 3N matrix which is given by (i) the linearization of the internal coordinates q (an algebraic process) and (ii) solution of Wilson's GF equations (a numeric process).

Read more about this topic:  GF Method

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