Extracting the electronic structure signal from X-ray and electron scattering in the gas phase

Journal article

X-ray and electron scattering from free gas-phase molecules is examined using the independent atom model (IAM) and ab initio electronic structure calculations. The IAM describes the effect of the molecular geometry on the scattering, but does not account for the redistribution of valence electrons due to, for instance, chemical bonding. By examining the total, i.e. energy-integrated, scattering from three molecules, fluoroform (CHF3), 1,3-cyclohexadiene (C6H8) and naphthalene (C10H8), the effect of electron redistribution is found to predominantly reside at small-to-medium values of the momentum transfer (q ≤ 8 Å−1) in the scattering signal, with a maximum percent difference contribution at 2 ≤ q ≤ 3 Å−1. A procedure to determine the molecular geometry from the large-q scattering is demonstrated, making it possible to more clearly identify the deviation of the scattering from the IAM approximation at small and intermediate q and to provide a measure of the effect of valence electronic structure on the scattering signal

Authors: Northey, T; Kirrander, A; Weber, PM

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: International Union of Crystallography
• Journal: Journal of Synchrotron Radiation
• Volume: 31
• Issue: 2
• Pages: 303-311
• Publication date: 2024-02-22
• Acceptance date: 2024-01-03
• DOI: 10.1107/s1600577524000067
• EISSN: 1600-5775
• ISSN: 0909-0495
• Language: English
• Keywords: Molecule; Momentum transfer; Computational chemistry; Scattering; Physics; Ab initio; Electron scattering; Electronic structure; Optics; Molecular physics; Electron; Valence electron; Valence (chemistry); Quantum mechanics; Chemistry; Atomic physics