• Genoni, Alessandro
• Kleemiss, Florian
• Hupf, Emanuel
• Grabowsky, Simon
• Borrmann, Tobias
• Pal, Rumpa
• Krzeszczakowska, Joanna M.
• Woińska, Magdalena

Abstract

<p>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.</p>

Topics

• impedance spectroscopy
• x-ray diffraction
• experiment
• extraction