Relativistic Hirshfeld atom refinement of an organo-gold(I) compound

Sylwia Pawledzio; Maura Malinska; Magdalena Woinska; Jakub Wojciechowski; Lorraine Andrade Malaspina; Florian Kleemiss; Simon Grabowsky; Krzysztof Wozniak

doi:10.1107/S2052252521004541

Relativistic Hirshfeld atom refinement of an organo-gold(I) compound

Sylwia Pawledzio, Maura Malinska, Magdalena Woinska, Jakub Wojciechowski, Lorraine Andrade Malaspina, Florian Kleemiss, Simon Grabowsky, Krzysztof Wozniak

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

The main goal of this study is the validation of relativistic Hirshfeld atom refinement (HAR) as implemented in Tonto for high-resolution X-ray diffraction datasets of an organo-gold(I) compound. The influence of the relativistic effects on statistical parameters, geometries and electron density properties was analyzed and compared with the influence of electron correlation and anharmonic atomic motions. Recent work in this field has indicated the importance of relativistic effects in the static electron density distribution of organo-mercury compounds. This study confirms that differences in electron density due to relativistic effects are also of significant magnitude for organo-gold compounds. Relativistic effects dominate not only the core region of the gold atom, but also influence the electron density in the valence and bonding region, which has measurable consequences for the HAR refinement model parameters. To study the effects of anharmonic motion on the electron density distribution, dynamic electron density difference maps were constructed. Unlike relativistic and electron correlation effects, the effects of anharmonic nuclear motion are mostly observed in the core area of the gold atom.

Original language	English
Pages (from-to)	608-620
Number of pages	13
Journal	IUCrJ
Volume	8
DOIs	https://doi.org/10.1107/S2052252521004541
State	Published - Jul 1 2021
Externally published	Yes

Funding

Support from the National Science Centre, Poland within PRELUDIUM grant No. UMO-2018/31/N/ST4/02141 and the University’s Integrated Development Programme (ZIP), cofinanced by the European Social Fund within the framework of the Operational Programme Knowledge Education Development 2016–2020 action 3.5, are gratefully acknowledged. This work was partly carried out at the Biological and Chemical Research Centre, University of Warsaw, established within the project co-financed by European Union from the European Regional Development Fund under the Operational Programme Innovative Economy, 2007–2013. The work was accomplished at the TEAM TECH Core Facility for crystallographic and biophysical research to support the development of medicinal products sponsored by the Foundation for Polish Science (grant No. 115). The synchrotron radiation experiments were performed at the BL02B1 beam-line of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal No. 2019A1069). Theoretical calculations were performed at the Wrocław Centre for Networking and Supercomputing infrastructure (grant No. 115).

Funders	Funder number
European Commission
Fundacja na rzecz Nauki Polskiej	115
Narodowym Centrum Nauki	UMO-2018/31/N/ST4/02141
European Social Fund
European Regional Development Fund

Keywords

Hirshfeld atom refinement
aspherical atom model
relativistic effects

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10.1107/S2052252521004541

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title = "Relativistic Hirshfeld atom refinement of an organo-gold(I) compound",

abstract = "The main goal of this study is the validation of relativistic Hirshfeld atom refinement (HAR) as implemented in Tonto for high-resolution X-ray diffraction datasets of an organo-gold(I) compound. The influence of the relativistic effects on statistical parameters, geometries and electron density properties was analyzed and compared with the influence of electron correlation and anharmonic atomic motions. Recent work in this field has indicated the importance of relativistic effects in the static electron density distribution of organo-mercury compounds. This study confirms that differences in electron density due to relativistic effects are also of significant magnitude for organo-gold compounds. Relativistic effects dominate not only the core region of the gold atom, but also influence the electron density in the valence and bonding region, which has measurable consequences for the HAR refinement model parameters. To study the effects of anharmonic motion on the electron density distribution, dynamic electron density difference maps were constructed. Unlike relativistic and electron correlation effects, the effects of anharmonic nuclear motion are mostly observed in the core area of the gold atom.",

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AU - Malinska, Maura

AU - Woinska, Magdalena

AU - Wojciechowski, Jakub

AU - Malaspina, Lorraine Andrade

AU - Kleemiss, Florian

AU - Grabowsky, Simon

AU - Wozniak, Krzysztof

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N2 - The main goal of this study is the validation of relativistic Hirshfeld atom refinement (HAR) as implemented in Tonto for high-resolution X-ray diffraction datasets of an organo-gold(I) compound. The influence of the relativistic effects on statistical parameters, geometries and electron density properties was analyzed and compared with the influence of electron correlation and anharmonic atomic motions. Recent work in this field has indicated the importance of relativistic effects in the static electron density distribution of organo-mercury compounds. This study confirms that differences in electron density due to relativistic effects are also of significant magnitude for organo-gold compounds. Relativistic effects dominate not only the core region of the gold atom, but also influence the electron density in the valence and bonding region, which has measurable consequences for the HAR refinement model parameters. To study the effects of anharmonic motion on the electron density distribution, dynamic electron density difference maps were constructed. Unlike relativistic and electron correlation effects, the effects of anharmonic nuclear motion are mostly observed in the core area of the gold atom.

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Relativistic Hirshfeld atom refinement of an organo-gold(I) compound

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Keywords

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