Pawlędzio Sylwia, Malinska Maura, Kleemiss Florian, Grabowsky Simon, Woźniak Krzysztof
Biological and Chemical Research Centre, Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, Warsaw 02-089, Poland.
Faculty for Chemistry und Pharmacy, University of Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany.
IUCrJ. 2022 Jun 11;9(Pt 4):497-507. doi: 10.1107/S2052252522005309. eCollection 2022 Jul 1.
Details of the validation of disorder modelling with Hirshfeld atom refinement (HAR) for a previously investigated organo-gold(I) compound are presented here. The impact of refining disorder on HAR results is discussed using an analysis of the differences of dynamic structure factors. These dynamic structure factor differences are calculated from thermally smeared quantum mechanical electron densities based on wavefunctions that include or exclude electron correlation and relativistic effects. When disorder is modelled, the electron densities stem from a weighted superposition of two (or more) different conformers. Here this is shown to impact the relative importance of electron correlation and relativistic effect estimates expressed by the structure factor magnitudes. The role of disorder modelling is also compared with the effect of the treatment of hydrogen anisotropic displacement parameter (ADP) values and atomic anharmonicity of the gold atom. The analysis of ADP values of gold and disordered carbon atoms showed that the effect of disorder significantly altered carbon ADP values and did not influence those of the gold atom.
本文介绍了对一种先前研究过的有机金（I）化合物进行基于 Hirshfeld 原子精修（HAR）的无序建模验证的详细情况。通过分析动态结构因子的差异，讨论了精修无序对 HAR 结果的影响。这些动态结构因子差异是根据基于包含或排除电子关联和相对论效应的波函数的热弥散量子力学电子密度计算得出的。当对无序进行建模时，电子密度源于两种（或更多）不同构象的加权叠加。在此表明，这会影响由结构因子大小表示的电子关联和相对论效应估计的相对重要性。还将无序建模的作用与氢各向异性位移参数（ADP）值处理和金原子的原子非谐性的影响进行了比较。对金和无序碳原子的 ADP 值分析表明，无序的影响显著改变了碳的 ADP 值，而对金原子的 ADP 值没有影响。
