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Next: The Triplet Relation from Sayre's Equation
Up: An Introduction to Direct Methods. The
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If two reflections H and K are both strong then the electron density is
likely to be found in the neighbourhood of the two sets of equidistant planes
defined by H and K. That is to say the electron density will be found near
the lines of intersection of the planes H and K as indicated in projection
in Fig. 9. A large |E| for reflection -H-K as well implies that the
electron density will also peak in planes lying d-H-K apart. It is
therefore most likely that these planes run through the lines of intersection of
the planes H and K, in other words that the three sets of planes have their
lines of intersection in common (see Fig. 10a). Then by choosing an origin at
an arbitrary point the triplet phase relationship can be found from a
planimetric theorem, proved in Fig. 11:
|
AO/AD + BO/BE + CO/CF = 2
|
(14) |
which is equivalent to
| |
(15) |
Because the choice of the origin is arbitrary it is obvious that expression (15)
is independent of the position of the origin: relations of this type are usually
called `structure invariants', although a more logical name would be `origin
invariants'.
Figure 8:
A few large terms (I: FKFH-K; II: FK'FH-K'; etc) from the
right hand side of expression (27) in a phase diagram. It can be seen that
their phases (1: ; 2: ; etc) are
approximately equal to .
|
Figure 9:
If the reflections H and K are both strong, then the electron
density will likely lie in the neighbourhood of the intersecting lines of the
two sets of equidistant planes defined by H and K.
|
Figure 10:
When H and K are strong and -H-K is strong as well it is more
likely that the planes of high density of -H-K run through the lines of
intersection (a) than just in betwen (b).
|
Figure 11:
In an arbitrary triangle ABC an origin O has been arbitrarily
drawn.
Theorem: AO/AD + BO/BE + CO/CF = 2.
Proof: AO/AD = AP/AC; CO/CF = CR/AC; BO/BE = BQ/BC = AS/AC; because
RP = SC, AP + CR +AS = 2AC.
|
In Fig. 10a the ideal situation is sketched and of course a small shift of the
planes of largest density of -H-K does not affect the reasoning given above.
However, the most unlikely position for these planes is the one indicated in
Fig. 10b; here the planes -H-K of largest electron density keep clear of the
lines of intersection of H and K. The triplet relationship therefore has a
probability character and this is emphasised by formulating it as
| |
(16) |
for large values of E3 = N-1/2|EHEKE-H-K|. The -sign means
that the most probable value of the triplet phase sum is 0. Clearly, the
triplet product E3 is large when all three reflections H, K and -H-K have
large |E|-values.
Next: The Triplet Relation from Sayre's Equation
Up: An Introduction to Direct Methods. The
Previous: The -Relation from a Harker-Kasper Inequality
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