Relativistic quantum crystallography of diphenyl- and dicyanomercury. Theoretical structure factors and Hirshfeld atom refinement

Bučinský, Lukáš; Jayatilaka, Dylan; Grabowsky, Simon (2019). Relativistic quantum crystallography of diphenyl- and dicyanomercury. Theoretical structure factors and Hirshfeld atom refinement. Acta Crystallographica Section A Foundations and Advances, 75(5), pp. 705-717. International Union of Crystallography 10.1107/S2053273319008027

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Quantum crystallographic refinement of heavy‐element‐containing compounds is a challenge, because many physical effects have to be accounted for adequately. Here, the impact and magnitude of relativistic effects are compared with those of electron correlation, polarization through the environment, choice of basis set and treatment of thermal motion effects on the structure factors of diphenylmercury(II) [Hg(Ph)2] and dicyanomercury(II) [Hg(CN)2]. Furthermore, the individual atomic contributions to the structure factors are explored in detail (using Mulliken population analysis and the exponential decay of atomic displacement parameters) to compare the contributions of lighter atoms, especially hydrogen atoms, against mercury. Subsequently, relativistic Hirshfeld atom refinement (HAR) is validated against theoretical structure factors of Hg(Ph)2 and Hg(CN)2, starting from perturbed geometries, to test if the relativistic variant of HAR leads to multiple solutions. Generally, relativistic HAR is successful, leading to a perfect match with the reference geometries, but some limitations are pointed out.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Grabowsky, Simon

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

2053-2733

Publisher:

International Union of Crystallography

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

20 Jan 2020 10:58

Last Modified:

20 Jan 2020 10:58

Publisher DOI:

10.1107/S2053273319008027

BORIS DOI:

10.7892/boris.138387

URI:

https://boris.unibe.ch/id/eprint/138387

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