International
Tables for
Crystallography
Volume B
Reciprocal space
Edited by U. Shmueli

International Tables for Crystallography (2006). Vol. B. ch. 2.1, pp. 208-209   | 1 | 2 |

Section 2.1.8.7. Comparison of the correction-factor and Fourier approaches

U. Shmuelia* and A. J. C. Wilsonb

aSchool of Chemistry, Tel Aviv University, Tel Aviv 69 978, Israel, and bSt John's College, Cambridge, England
Correspondence e-mail:  ushmueli@post.tau.ac.il

2.1.8.7. Comparison of the correction-factor and Fourier approaches

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The need for theoretical non-ideal distributions was exemplified by Fig. 2.1.7.1(a), referred to above, and the performance of the two approaches described above, for this particular example, is shown in Fig. 2.1.7.1(b). Briefly, the Fourier p.d.f. shows an excellent agreement with the histogram of recalculated values, while the agreement attained by the Hermite correction factor is much less satisfactory, even for the (longest available to us) five-term expansion. It must be pointed out that (i) the inadequacy of `short' correction factors, in the example shown, is due to the large deviation from the ideal behaviour and (ii) the number of terms used there in the Fourier summation is twenty, whereafter the summation is terminated. Obviously, the computation of twenty (or more) Fourier coefficients is easier than that of five terms in the correction factor. The convergence of the Fourier series is very satisfactory. It appears that the (analytically) exact Fourier approach is the preferred one in cases of large or intermediate deviations, while the correction-factor approach may cope well with small ones. As far as the availability of symmetry-dependent centric and acentric p.d.f.'s is concerned, correction factors are available for all the space groups (see Table 2.1.7.1), while Fourier coefficients of p.d.f.'s are available for the first 206 space groups (see Table 2.1.8.1). It should be pointed out that p.d.f.'s based on the correction-factor method cope very well with cubic symmetries higher than , even if the asymmetric unit of the space group is strongly heterogeneous (Rabinovich et al., 1991b).

Both approaches described in this section are related to the characteristic function of the required p.d.f. The correction-factor p.d.f.'s (2.1.7.5) and (2.1.7.6) can be obtained by expanding the logarithm of the appropriate characteristic function in a series of cumulants [e.g. equation (2.1.4.13); see also Shmueli & Wilson (1982)], truncating the series and performing its term-by-term Fourier inversion. The Fourier p.d.f., on the other hand, is computed by forming a Fourier series whose coefficients are exact analytical forms of the characteristic function at points related to the summation indices [e.g. equations (2.1.8.5), (2.1.8.9) and (2.1.8.11), and Table 2.1.8.1] and truncating the series when the terms become small enough.

References

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Rabinovich, S., Shmueli, U., Stein, Z., Shashua, R. & Weiss, G. H. (1991b). Exact random-walk models in crystallographic statistics. VII. An all-space-group study of the effects of atomic heterogeneity on the p.d.f.'s of . Acta Cryst. A47, 336–340.Google Scholar
Shmueli, U. & Wilson, A. J. C. (1982). Intensity statistics: non-ideal distributions in theory and practice. In Crystallographic statistics: progress and problems, edited by S. Ramaseshan, M. F. Richardson & A. J. C. Wilson, pp. 83–97. Bangalore: Indian Academy of Sciences.Google Scholar