Back to overview

Unconstrained and X-ray constrained Extremely Localized Molecular Orbitals: analysis of the reconstructed electron density

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Publication date 2014
Author Rezende Dos Santos Leonardo Humberto, Genoni Alessandro, Macchi Piero,
Project Properties of metal-organic materials from accurate electron density determination
Show all

Original article (peer-reviewed)

Journal Acta Crystallographica, section A
Volume (Issue) A70
Page(s) 532 - 551
Title of proceedings Acta Crystallographica, section A
DOI 10.1107/S2053273314019652

Open Access

Type of Open Access Repository (Green Open Access)


The recently developed X-ray constrained extremely localized molecular orbital (XC-ELMO) technique is a potentially useful tool for the determination and analysis of experimental electron densities. Molecular orbitals strictly localized on atoms, bonds or functional groups allow one to combine the quantum-mechanical rigour of the wavefunction-based approaches with the easy chemical interpretability typical of the traditional multipole models. In this paper, using very high quality X-ray diffraction data for the glycylglycine crystal, a detailed assessment of the capabilities and limitations of this new method is given. In particular, the effects of constraining the ELMO wavefunctions to experimental X-ray structure-factor amplitudes and the ability of the method to reproduce benchmark electron distributions have been accurately investigated. Topological analysis of the XC-ELMO electron densities and of the zero-flux surface-integrated charges and dipole moments shows that the new strategy is already reliable, provided that sufficiently flexible basis sets are used. These analyses also raise new questions and call for further improvements of the method.