scholarly journals Computational study of An–X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis

2017 ◽  
Vol 46 (3) ◽  
pp. 760-769 ◽  
Author(s):  
Kieran T. P. O'Brien ◽  
Nikolas Kaltsoyannis
Keyword(s):  
Quantum Theory ◽  
Bond Energy ◽  
Computational Study ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
P Element ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Block Based

Good correlations are found between QTAIM BCP and EDA data for a range of Th(iv)- and Th(iii)-p element bonds.

scholarly journals Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments

2018 ◽  
Vol 9 (12) ◽  
pp. 3111-3121 ◽  
Author(s):  
Felix Engelhardt ◽  
Christian Maaß ◽  
Diego M. Andrada ◽  
Regine Herbst-Irmer ◽  
Dietmar Stalke
Keyword(s):  
Quantum Theory ◽  
Dft Calculations ◽  
Charge Density ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Lithium Amide ◽  
Experimental Charge Density ◽  
Amide Versus

We investigated [{(Me2NCH2)2(C4H2N)}Li]2 (1) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA).

scholarly journals A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5175
Author(s):  
Sławomir J. Grabowski
Keyword(s):  
Quantum Theory ◽  
Molecular Hydrogen ◽  
Natural Bond Orbital ◽  
Decomposition Analysis ◽  
Lewis Base ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Halogen Bonds ◽  
Structural Database ◽  
Base Units

CCSD(T)/aug-cc-pVTZ//ωB97XD/aug-cc-pVTZ calculations were performed for halogen-bonded complexes. Here, the molecular hydrogen, cyclopropane, cyclobutane and cyclopentane act as Lewis base units that interact through the electrons of the H–H or C–C σ-bond. The FCCH, ClCCH, BrCCH and ICCH species, as well as the F2, Cl2, Br2 and I2 molecular halogens, act as Lewis acid units in these complexes, interacting through the σ-hole localised at the halogen centre. The Quantum Theory of Atoms in Molecules (QTAIM), the Natural Bond Orbital (NBO) and the Energy Decomposition Analysis (EDA) approaches were applied to analyse these aforementioned complexes. These complexes may be classified as linked by A–X···σ halogen bonds, where A = C, X (halogen). However, distinct properties of these halogen bonds are observed that depend partly on the kind of electron donor: dihydrogen, cyclopropane, or another cycloalkane. Examples of similar interactions that occur in crystals are presented; Cambridge Structural Database (CSD) searches were carried out to find species linked by the A–X···σ halogen bonds.

scholarly journals Intramolecular Hydrogen Bond Energy and Its Decomposition—O–H∙∙∙O Interactions

Crystals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 5
Author(s):  
Sławomir J. Grabowski
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Intramolecular Hydrogen Bond ◽  
Bond Energy ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Intermolecular Hydrogen Bonds ◽  
Hydrogen Bond Energy ◽  
Intramolecular Hydrogen

The method to calculate the energy of intramolecular hydrogen bond is proposed and tested for a sample of malonaldehyde and its fluorine derivatives; the corresponding calculations were performed at the ωB97XD/aug-cc-pVTZ level. This method based on relationships found for related intermolecular hydrogen bonds is compared with other approaches which may be applied to estimate the intramolecular hydrogen bond energy. Particularly, methods based on the comparison of the system that contains the intramolecular hydrogen bond compared with corresponding conformations where such interaction does not occur are discussed. The function-based energy decomposition analysis, FB-EDA, of the intramolecular hydrogen bonds is also proposed here.

Characterization of fluorine-centred `F...O' σ-hole interactions in the solid state

2017 ◽  
Vol 73 (2) ◽  
pp. 140-152 ◽  
Author(s):  
Abhishek Sirohiwal ◽  
Venkatesha R. Hathwar ◽  
Dhananjay Dey ◽  
Roshni Regunathan ◽  
Deepak Chopra
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Interaction Analysis ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Topological Features ◽  
Atomic Polarizability

In the current study, the crystal structure of 1-(3-nitrophenyl)-2,2,2-trifluoroethanone (A1) and (E)-4-((4-fluorophenyl) diazenyl)phenol (A2) has been analyzed for the characterization of the presence of a `unique' and `rare' intermolecular C(sp3/sp2)—F...O contact, which has been observed to play a significant role in the crystal packing. Theoretical charge-density calculations have been performed to study the nature and strength associated with the existence of this intermolecular F...O contact, wherein the F atom is attached to ansp3-hybridized C atom in the case of A1 and to ansp2hybridized carbon in the case of A2. The crystal packing of the former contains two `electronically different' Csp3—F...O contacts which are present across and in between the layers of molecules. In the latter case, it is characterized by the presence of a very `short' (2.708 Å) and `highly directional' (168° at ∠C4—F1...O1 and 174° at ∠C10—O1...F1) Csp2—F...O contact. According to the Cambridge Structural Database (CSD) study, it is a rare example in molecular crystals. Topological features of F...O contacts in the solid state were compared with the gas-phase models. The two-dimensional and three-dimensional static deformation density obtained from theoretical multipole modeling confirm the presence of a charge depleted region on the F atoms. Minimization of the electrostatic repulsion between like charges are observed through subtle arrangements in the electronic environment in two of the short intermolecular F...O contacts. These contacts were investigated using inputs from pair energy decomposition analysis, Bader's quantum theory of atoms in molecules (QTAIM), Hirshfeld surface analysis, delocalization index, reduced density gradient (RDG) plot, electrostatic potential surface and distributed atomic polarizability. The intermolecular energy decomposition (PIXEL) and RDG–NCI (non-covalent interaction) analysis of the F...O contacts establish the interaction to be dispersive in nature. The mutual polarization of an O atom by fluorine andviceversaprovides real physical insights into the role of atomic polarizability in interacting atoms in molecules in crystals.

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