On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system
In this study, the flexibility of the multipole Hansen–Coppens (HC) model refinement is investigated on calculated structure factors from a DFT reference for the tetrakis(μ-acetato)diaquadicopper model system (CCDC reference 1811668). The effect of the resolution [sin(θ)/λ], the Cu scattering factor...
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International Union of Crystallography
2025-07-01
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| Online Access: | https://journals.iucr.org/paper?S2052252525003355 |
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| author | Andrej Hlinčík Tadeáš Fülöp Peter Herich Jozef Kožíšek Karol Lušpai Lukáš Bučinský |
| author_facet | Andrej Hlinčík Tadeáš Fülöp Peter Herich Jozef Kožíšek Karol Lušpai Lukáš Bučinský |
| author_sort | Andrej Hlinčík |
| collection | DOAJ |
| description | In this study, the flexibility of the multipole Hansen–Coppens (HC) model refinement is investigated on calculated structure factors from a DFT reference for the tetrakis(μ-acetato)diaquadicopper model system (CCDC reference 1811668). The effect of the resolution [sin(θ)/λ], the Cu scattering factor, the inclusion of anisotropic displacement parameters and the positions of the atoms in the refinement are considered in terms of statistical error analysis, residual and deformation density maps, Atoms In Molecules parameters, d-orbital populations, and others. The choice of the neutral Cu scattering factor in the HC refinement is found to give the most satisfactory results for most of the monitored parameters, despite the formal Cu2+ nature of copper in the studied complex. In order to put the difference between the HC model and the reference DFT (BLYP functional) results on the right scale, several computational chemistry methods (B3LYP, Hartree–Fock, Møller–Plesset perturbation theory and Coupled Clusters Singles and Doubles) were compared with the chosen DFT reference. Differences in the magnitudes of the structure factors and AIM parameters are presented, including considerations of relativistic effects and periodic boundary conditions, i.e. a comparison of a molecular crystal calculation versus an isolated molecule in the crystal. |
| format | Article |
| id | doaj-art-27febdb8a2e04554afd4f6e1877f93c8 |
| institution | DOAJ |
| issn | 2052-2525 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | International Union of Crystallography |
| record_format | Article |
| series | IUCrJ |
| spelling | doaj-art-27febdb8a2e04554afd4f6e1877f93c82025-08-20T02:43:09ZengInternational Union of CrystallographyIUCrJ2052-25252025-07-0112444446110.1107/S2052252525003355pen5009On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model systemAndrej Hlinčík0Tadeáš Fülöp1Peter Herich2Jozef Kožíšek3Karol Lušpai4Lukáš Bučinský5Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37, Bratislava, Slovak RepublicIn this study, the flexibility of the multipole Hansen–Coppens (HC) model refinement is investigated on calculated structure factors from a DFT reference for the tetrakis(μ-acetato)diaquadicopper model system (CCDC reference 1811668). The effect of the resolution [sin(θ)/λ], the Cu scattering factor, the inclusion of anisotropic displacement parameters and the positions of the atoms in the refinement are considered in terms of statistical error analysis, residual and deformation density maps, Atoms In Molecules parameters, d-orbital populations, and others. The choice of the neutral Cu scattering factor in the HC refinement is found to give the most satisfactory results for most of the monitored parameters, despite the formal Cu2+ nature of copper in the studied complex. In order to put the difference between the HC model and the reference DFT (BLYP functional) results on the right scale, several computational chemistry methods (B3LYP, Hartree–Fock, Møller–Plesset perturbation theory and Coupled Clusters Singles and Doubles) were compared with the chosen DFT reference. Differences in the magnitudes of the structure factors and AIM parameters are presented, including considerations of relativistic effects and periodic boundary conditions, i.e. a comparison of a molecular crystal calculation versus an isolated molecule in the crystal.https://journals.iucr.org/paper?S2052252525003355hansen–coppens modelmultipole modelbenchmarkingdensity functional theorydftab initio studiesexperimental errorscomputational modelingmolecular crystalsmaterials modelingmolecular simulations |
| spellingShingle | Andrej Hlinčík Tadeáš Fülöp Peter Herich Jozef Kožíšek Karol Lušpai Lukáš Bučinský On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system IUCrJ hansen–coppens model multipole model benchmarking density functional theory dft ab initio studies experimental errors computational modeling molecular crystals materials modeling molecular simulations |
| title | On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system |
| title_full | On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system |
| title_fullStr | On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system |
| title_full_unstemmed | On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system |
| title_short | On the flexibility of the multipole model refinement. A DFT benchmark study of the tetrakis(μ-acetato)diaquadicopper model system |
| title_sort | on the flexibility of the multipole model refinement a dft benchmark study of the tetrakis μ acetato diaquadicopper model system |
| topic | hansen–coppens model multipole model benchmarking density functional theory dft ab initio studies experimental errors computational modeling molecular crystals materials modeling molecular simulations |
| url | https://journals.iucr.org/paper?S2052252525003355 |
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