The Advent of Quantum Crystallography: Form and Structure Factors from Quantum Mechanics for Advanced Structure Refinement and Wavefunction Fitting

  title={The Advent of Quantum Crystallography: Form and Structure Factors from Quantum Mechanics for Advanced Structure Refinement and Wavefunction Fitting},
  author={Simon Grabowsky and Alessandro Genoni and Sajesh P. Thomas and Dylan Jayatilaka},
  • 2022
Quantum mechanics/extremely localized molecular orbital embedding technique: Theoretical foundations and further validation
  • G. Macetti, A. Genoni
  • Chemistry
    New Electron Correlation Methods and their Applications, and Use of Atomic Orbitals with Exponential Asymptotes
  • 2021
H-Atom Assignment and Sb-O Bonding of [Mes3SbOH][O3SPh] Confirmed by Neutron Diffraction, Multipole Modeling, and Hirshfeld Atom Refinement.
Results confirm that [Mes3SbOH][O3SPh] does indeed feature a hydroxystibonium cation with a nominal Sb-O single bond and not a stibine oxide with an Sb=O/Sb+-O- bond.
Different Reactivities of (5-Ph2P-Ace-6-)2MeSiH toward the Rhodium(I) Chlorides [(C2H4)2RhCl]2 and [(CO)2RhCl]2. Hirshfeld Atom Refinement of a Rh–H···Si Interaction
The reaction of (5-Ph2P-Ace-6-)2MeSiH with [(C2H4)2RhCl]2 proceeded via elimination of ethylene and oxidative addition of the Si–H bond at rhodium and provided the rhodium(III) complex
The advanced treatment of hydrogen bonding in quantum crystallography
Hydrogen-bonding parameters are modelled with different methods of quantum crystallography. The underlying model assumptions are analysed and related to the refinement results.
lamaGOET: an interface for quantum crystallography
The program lamaGOET serves as an interface between quantum-mechanical and crystallographic refinement software to enhance the flexibility of the quantum-crystallographic methods Hirshfeld atom
Extending Libraries of Extremely Localized Molecular Orbitals to Metal Organic Frameworks: A Preliminary Investigation
Libraries of extremely localized molecular orbitals (ELMOs) have been recently assembled to reconstruct approximate wavefunctions of very large biological systems, such as polypeptides and proteins.
QM/ELMO: A Multi-Purpose Fully Quantum Mechanical Embedding Scheme Based on Extremely Localized Molecular Orbitals.
The recently proposed QM/ELMO (quantum mechanics/extremely localized molecular orbital) scheme is reviewed, namely a new multiscale embedding strategy in which the most chemically relevant region of the investigated system is treated at fully quantum chemical level, while the remaining part is described by means of transferred extremely localized molecular orbitals that remain frozen throughout the computation.
A Step toward the Quantification of Noncovalent Interactions in Large Biological Systems: The Independent Gradient Model-Extremely Localized Molecular Orbital Approach
The validation tests performed on small polypeptides and peptide dimers have shown that the novel IGM-ELMO strategy provides results that are systematically closer to the fully quantum mechanical ones and outperforms the IGM method based on the crude promolecular approximation, but still keeping a quite low computational cost.
Quantum Mechanics/Extremely Localized Molecular Orbital Embedding Strategy for Excited States: Coupling to Time-Dependent Density Functional Theory and Equation-of-Motion Coupled Cluster.
This work presents the coupling of the QM/ELMO philosophy with Time-Dependent Density Functional Theory (TDDFT) and Equation-of-Motion Coupled Cluster with single and double substitutions (EOM-CCSD), and suggests the coupling with other quantum chemical strategies for excited states.


Powder diffraction
The powder diffraction method, by using conventional X-ray sources, was devised independently in 1916 by Debye and Scherrer in Germany and in 1917 by Hull in the United States. The technique
Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density
Resonance-assisted hydrogen bonds (RAHBs) are exploited in chemical synthesis or serve as models for biologically relevant proton-transfer reactions [K. T. Mahmudov and A. J. L. Pombeiro, Chem. –
On the use of the Obara-Saika recurrence relations for the calculation of structure factors in quantum crystallography.
  • A. Genoni
  • Chemistry
    Acta crystallographica. Section A, Foundations and advances
  • 2020
It is shown that the Fourier integrals can be efficiently calculated by exploiting an extension of the Obara-Saika recurrence formulas, which are successfully used by quantum chemists in the computation of molecular integrals.
Crystallographic Refinement using Non-Spherical Form Factors in olex2.refine
We have implemented a procedure that allows the use of non-spherical atomic form factors in a standard crystallographic X-Ray refinement. We outline the procedure for their use, alongside a
Experimental Insights into the Electronic Nature, Spectral Features, and Role of Entropy in Short CH3···CH3 Hydrophobic Interactions.
For the first time, the solid-state entropic contribution from the torsional mode of the methyl groups in stabilizing these interactions is quantified by thermal motion analysis based on neutron diffraction as well as variable-temperature crystallography.
NCI-ELMO: a New Method to Quickly and Accurately Detect Non-Covalent Interactions in Biosystems.
A new tool for the efficient identification of non-covalent interactions in proteins by leveraging the libraries of extremely localized molecular orbitals (ELMOs), which allow instantaneous reconstruction of quantum mechanically rigorous electron distributions of polypeptides and proteins.
X-ray constrained spin-coupled technique: theoretical details and further assessment of the method.
A detailed theoretical derivation of the fundamental equations at the basis of the XCSC method is provided and a further advancement of its original version is introduced, mainly consisting in the use of molecular orbitals resulting from XCW calculations at the Hartree-Fock level to describe the inactive electrons in theXCSC computations.
Fast and Accurate Quantum Crystallography: from Small to Large, from Light to Heavy.
The coupling of the crystallographic refinement method Hirshfeld Atom Refinement (HAR) with the recently constructed libraries of extremely localized molecular orbitals (ELMOs) gives rise to the new
Relativistic quantum crystallography of diphenyl- and dicyanomercury. Theoretical structure factors and Hirshfeld atom refinement.
The impact and magnitude of relativistic effects are compared with those of electron correlation, polarization through the environment, choice of basis set and treatment of thermal motion effects on the structure factors of diphenylmercury( II) [Hg(Ph)2] and dicyanomercury(II) [ Hg(CN)2].