Artykuł w czasopiśmie
Brak miniatury
Licencja
ClosedAccessDostęp zamknięty
 

How do density functionals affect the Hirshfeld atom refinement?

Uproszczony widok
cris.lastimport.scopus2024-02-12T19:38:42Z
dc.abstract.enIn this work, the effect of mixing different amounts of Hartree–Fock (HF) exchange with hybrid density functionals applied to the Hirshfeld atom refinement (HAR) of urea and oxalic acid dihydrate is explored. Together, the influence of using different basis sets, methods (including MP2 and HF) and cluster sizes (to model bulk effects) is studied. The results show that changing the amount of HF exchange, no matter the level of theory, has an impact almost exclusively on the H atom refinement parameters. Contrary to pure quantum mechanical calculations where good geometries are obtained with intermediate HF exchange mixtures, in the HAR the best match with neutron diffraction reference values is not necessarily found for these admixtures. While the non-hydrogen covalent bond lengths are insensitive to the combination of method or basis set employed, the X–H bond lengths always increase proportionally to the HF exchange for the analysed systems. This outcome is opposite to what is normally observed from geometry optimisations, i.e., shorter bonds are obtained with greater HF exchange. Additionally, the thermal ellipsoids tend to shrink with larger HF exchange, especially for the H atoms involved in strong hydrogen bonding. Thus, it may be the case that the development of density functionals or basis sets suitable for quantum crystallography should take a different path than those fitted for quantum chemistry calculations.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorContreras-García, Julia
dc.contributor.authorDominiak, Paulina
dc.contributor.authorCortés-Guzmán, Fernando
dc.contributor.authorRamírez-Palma, David
dc.contributor.authorLanderos-Rivera, Bruno
dc.date.accessioned2024-01-25T03:29:43Z
dc.date.available2024-01-25T03:29:43Z
dc.date.issued2023
dc.description.financePublikacja bezkosztowa
dc.identifier.doi10.1039/D2CP04098K
dc.identifier.issn1463-9076
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/108647
dc.identifier.weblinkhttp://pubs.rsc.org/en/content/articlepdf/2023/CP/D2CP04098K
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofPhysical Chemistry Chemical Physics
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.titleHow do density functionals affect the Hirshfeld atom refinement?
dc.typeJournalArticle
dspace.entity.typePublication