Hupf, Emanuel and Kleemiss, Florian and Borrmann, Tobias and Pal, Rumpa and Krzeszczakowska, Joanna M. M. and Woinska, Magdalena and Jayatilaka, Dylan and Genoni, Alessandro and Grabowsky, Simon (2023) The effects of experimentally obtained electron correlation and polarization on electron densities and exchange-correlation potentials. JOURNAL OF CHEMICAL PHYSICS, 158 (12): 124103. ISSN 0021-9606, 1089-7690
Full text not available from this repository. (Request a copy)Abstract
In X-ray constrained wavefunction (XCW) fitting, external information, such as electron correlation and polarization, is included into a single-determinantal isolated-molecule wavefunction. In a first step, we show that the extraction of these two physical effects by XCW fitting is complete and accurate by comparing to theoretical reference calculations. In a second step, we show that fitting to data from single-crystal x-ray diffraction measurements provides the same results qualitatively and how the physical effects can be separated, although always inherently convolved in the experiment. We further demonstrate that exchange-correlation potentials are systematically affected by XCW fitting in a physically meaningful way, which could be exploited for method development in quantum chemistry, subject to some remaining challenges that we also outline.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | X-RAY-DIFFRACTION; WAVE-FUNCTIONS; CHARGE-DENSITY; TOPOLOGICAL PROPERTIES; CORRELATION FUNCTIONALS; REFINEMENT STRATEGIES; DISTRIBUTIONS; MOLECULE; BOND; APPROXIMATION |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Central Analytical Services |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 20 Mar 2024 07:21 |
| Last Modified: | 20 Mar 2024 07:21 |
| URI: | https://pred.uni-regensburg.de/id/eprint/60693 |
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