Is there a future for topological analysis in experimental charge-density research?

2017 ◽  
Vol 73 (3) ◽  
pp. 325-329 ◽  
Author(s):  
Birger Dittrich
Keyword(s):  
Charge Density ◽  
Intermolecular Interaction ◽  
Intermolecular Interactions ◽  
Chemical Bonding ◽  
Topological Analysis ◽  
Theoretical Chemistry ◽  
Research Tool ◽  
Interaction Energies ◽  
Research Focus ◽  
Experimental Charge Density

Topological analysis using Bader and co-worker'sAtoms in Moleculestheory has seen many applications in theoretical chemistry and experimental charge-density research. A brief overview of successful early developments, establishing topological analysis as a research tool for characterizing intramolecular chemical bonding, is provided. A lack of vision in many `descriptive but not predictive' subsequent studies is discussed. Limitations of topology for providing accurate energetic estimates of intermolecular interaction energies are put into perspective. It is recommended that topological analyses of well understood bonding situations are phased out and are only reported for unusual bonding. Descriptive studies of intermolecular interactions should have a clear research focus.

X·F (X=C, N, O and S) Noncovalent Weak Intermolecular Interactions

2014 ◽  
Vol 881-883 ◽  
pp. 192-195
Author(s):  
Yan Zhi Liu ◽  
Huian Tang
Keyword(s):  
Intermolecular Interaction ◽  
Electron Density ◽  
Intermolecular Interactions ◽  
Topological Analysis ◽  
Interaction Energies ◽  
Weak Intermolecular Interaction ◽  
Weak Intermolecular Interactions ◽  
The Stability ◽  
Bsse Correction ◽  
Computational Level

A number of X···F (X=C, N, O and S) noncovalent weak intermolecular interaction systems of CH3-F···XO2 (X=C, N, O and S) has been investigated at B3LYP/6-311++G(d, p) computational level. A topological analysis of the electron density for the X···F (X=C, N, O and S) noncovalent weak bonds was performed using Baders theory of atom-in-molecules (AIM). The interaction content of the F···X in H3CF···CO2 complex would mainly represent more π property than others. The interaction energies data without (ΔE) and with (ΔEcp) BSSE correction showed that the stability of the four complexes of the H3CF···DB2 system increases in the order of H3CF···O3 < H3CF···NO2 < H3CF···CO2 < H3CF···SO2.

Chemical bonding in pentaerythritol at very low temperature or at high pressure: an experimental and theoretical study

2006 ◽  
Vol 62 (3) ◽  
pp. 513-520 ◽  
Author(s):  
Elizabeth A. Zhurova ◽  
Vladimir G. Tsirelson ◽  
Vladimir V. Zhurov ◽  
Adam I. Stash ◽  
A. Alan Pinkerton
Keyword(s):  
High Pressure ◽  
Energy Density ◽  
Low Temperature ◽  
Intermolecular Interaction ◽  
Electron Density ◽  
Chemical Bonding ◽  
Topological Analysis ◽  
Interaction Energies ◽  
Molecular Layers ◽  
Very Low Temperature

Chemical bonding in the pentaerythritol crystal based on the experimental electron density at 15 (1) K, and theoretical calculations at the experimental molecular geometries obtained at room and low (15 K) temperatures have been analyzed and compared in terms of the topological analysis. Topological electron-density features corresponding to the high-pressure (1.15 GPa) geometry are also reported. In addition to the bond critical points (CPs) within the molecular layers, CPs between the atoms of different molecular layers have been located and the bonding character of these relatively weak interactions discussed. Atomic charges and energies have been integrated over the atomic basins delimited by the zero-flux surfaces, and the intermolecular interaction energies have been calculated. The interaction between molecular layers in the crystal becomes stronger both at very low temperature and high pressure, as demonstrated by the more negative intermolecular interaction energies, higher electron density and energy density values at the CPs, and sharper electronic-energy density profiles.

Revisiting the charge density analysis of 2,5-dichloro-1,4-benzoquinone at 20 K

2017 ◽  
Vol 73 (4) ◽  
pp. 654-659 ◽  
Author(s):  
Zhijie Chua ◽  
Bartosz Zarychta ◽  
Christopher G. Gianopoulos ◽  
Vladimir V. Zhurov ◽  
A. Alan Pinkerton
Keyword(s):  
Charge Density ◽  
Electron Density ◽  
Topological Analysis ◽  
Diffraction Measurement ◽  
X Ray Diffraction ◽  
Total Electron Density ◽  
Total Electron ◽  
Structure Factors ◽  
Density Analysis ◽  
Experimental Charge Density

A high-resolution X-ray diffraction measurement of 2,5-dichloro-1,4-benzoquinone (DCBQ) at 20 K was carried out. The experimental charge density was modeled using the Hansen–Coppens multipolar expansion and the topology of the electron density was analyzed in terms of the quantum theory of atoms in molecules (QTAIM). Two different multipole models, predominantly differentiated by the treatment of the chlorine atom, were obtained. The experimental results have been compared to theoretical results in the form of a multipolar refinement against theoretical structure factors and through direct topological analysis of the electron density obtained from the optimized periodic wavefunction. The similarity of the properties of the total electron density in all cases demonstrates the robustness of the Hansen–Coppens formalism. All intra- and intermolecular interactions have been characterized.

Experimental charge density in the transition metal complex Mn2(CO)10: a comparative study

2003 ◽  
Vol 59 (2) ◽  
pp. 234-247 ◽  
Author(s):  
Louis J. Farrugia ◽  
Paul R. Mallinson ◽  
Brian Stewart
Keyword(s):  
Charge Density ◽  
Transition Metal Complex ◽  
Topological Analysis ◽  
Atoms In Molecules ◽  
Topological Properties ◽  
B3lyp Level ◽  
Metal Metal ◽  
Density Study ◽  
Experimental Charge Density ◽  
Metal Ligand

An accurate experimental charge density study at 100 K of Mn2(CO)10 [bis(pentacarbonylmanganese)(Mn—Mn)] has been undertaken. A comparison with previously reported structural determinations reveals no evidence for significant Mn—Mn bond lengthening between 100 and 296 K. The nature of the metal–metal and metal–ligand atom interactions has been studied by topological analysis using the Atoms in Molecules (AIM) approach of Bader [(1990), Atoms in Molecules: a Quantum Theory.Oxford: Clarendon Press]. An analysis of the density ρ(r), the Laplacian of the density ∇2ρ(r b ) and the total energy densities H(r b ) at the bond critical points is used to classify all the chemical bonds as covalent in nature. The results are compared qualitatively and quantitatively with previous charge density studies on this molecule and DFT calculations at the 6-311+G* B3LYP level. The topological properties of the theoretical and experimental densities are in close agreement.

Weak intra- and intermolecular interactions in a binaphthol imine: an experimental charge-density study on (±)-8′-benzhydrylideneamino-1,1′-binaphthyl-2-ol

2009 ◽  
Vol 65 (6) ◽  
pp. 757-769 ◽  
Author(s):  
Louis J. Farrugia ◽  
Pavel Kočovský ◽  
Hans Martin Senn ◽  
Štěpán Vyskočil
Keyword(s):  
Charge Density ◽  
Intermolecular Interactions ◽  
Density Functional ◽  
Topological Analysis ◽  
Accurate Determination ◽  
Phenyl Group ◽  
X Ray Diffraction ◽  
Pairwise Interactions ◽  
Weak Intermolecular Interactions

The charge density in (±)-8′-benzhydrylideneamino-1,1′-binaphthyl-2-ol (1) has been studied experimentally using Mo Kα X-ray diffraction at 100 K, and by theory using density-functional thoery (DFT) calculations at the B3LYP/6-311++G** level. The nature of the weak intramolecular peri-C...N, CH...π, H...H and C(π)...C(π) interactions has been examined by topological analysis using the Quantum Theory of Atoms in Molecules (QTAIM) approach. An analysis of the density ρ(r), the Laplacian of the density ∇2ρ(r b) and other topological properties at the bond-critical points were used to classify these interactions. The study confirms the presence of the intramolecular CH...π interaction in (1), which was previously suspected on geometrical grounds. An analysis of the ellipticity profiles along the bond paths unambiguously shows the π-delocalization between the imine unit and one N-phenyl group. The weak intermolecular interactions in the crystal of (1) were examined experimentally and theoretically through the pairwise interactions of the seven independent dimeric pairs of (1) responsible for the set of unique intermolecular interactions, and also through examination of the Hirshfeld surface d norm property. The theoretical dimeric-pair calculations used the BLYP-D functional which supplements the exchange-correlational functional with an empirical dispersion term to provide a more accurate determination of the energies for the weak intermolecular interactions.

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