Content area

Abstract

The increase in the weighted agreement factor due to systematic errors in single‐crystal X‐ray and neutron diffraction experiments can be quantified precisely, provided the estimated standard uncertainties of the observed intensities, s.u.(Iobs), are sufficiently accurate. The increase in the weighted agreement factor quantifies the `costs' of the systematic errors. This is achieved by comparison with the lowest possible weighted agreement factor for the specific data set. Application to 314 published data sets from inorganic, metal–organic and organic compounds shows that systematic errors increase the weighted agreement factor by a surprisingly large factor of g = 3.31 (or more) in 50% of the small‐molecule data sets from the sample. Examples of twinning, disorder, neglect of bonding densities and low‐energy contamination are taken from the literature and examined with respect to the increase in the weighted agreement factor, which is typically less than three. The large value g = 3.31 for the supposedly simple case of rather small molecules, as opposed to macromolecules, is interpreted as a warning sign that there are not only the expected remaining systematic errors, like not‐modelled disorder, unrecognized twinning or neglect of bonding electrons or similar errors, but additionally a common systematic error of insufficiently accurate s.u.(Iobs). Inadequate s.u.(Iobs) may not just compromise the model parameters and model parameter errors; they are also a threat to the whole data quality evaluation procedure that relies crucially on adequate s.u.(Iobs).

Details

Identifier / keyword
Title
Two metrics for quantifying systematic errors in diffraction experiments: systematic errors in the variance of the observed intensities and agreement factor gap
Author
Henn, Julian 1 

 Germany 
Publication title
Volume
58
Issue
4
Pages
1174-1184
Publication year
2025
Publication date
Aug 2025
Section
Research Papers
Publisher
Blackwell Publishing Ltd.
Place of publication
Oxford
Country of publication
United Kingdom
Publication subject
ISSN
00218898
e-ISSN
16005767
Source type
Scholarly Journal
Language of publication
English
Document type
Journal Article
Publication history
 
 
Online publication date
2025-06-20
Milestone dates
2024-12-21 (Received); 2025-05-14 (Accepted)
Publication history
 
 
   First posting date
20 Jun 2025
ProQuest document ID
3236158598
Document URL
https://www.proquest.com/scholarly-journals/two-metrics-quantifying-systematic-errors/docview/3236158598/se-2?accountid=208611
Copyright
© 2025. This work is published under Creative Commons Attribution License~https://creativecommons.org/licenses/by/3.0/ (the "License"). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.
Last updated
2025-08-04
Database
ProQuest One Academic