Unusually Strong Interactions Mediated by Both .pi.-.pi. Stacking and CH-.pi. Interactions Present in the Dimer of Nickel(II) Complex Coordinated with n-Butyl-Substituted Salen

1995 ◽  
Vol 117 (8) ◽  
pp. 2377-2378 ◽  
Author(s):  
Kazuo Miyamura ◽  
Akiko Mihara ◽  
Takashi Fujii ◽  
Yohici Gohshi ◽  
Youichi Ishii
Keyword(s):  
Strong Interactions ◽  
Pi Stacking ◽  
Pi Interactions

scholarly journals Reinterpreting π-Stacking

2020 ◽  
Author(s):  
Kevin Carter-Fenk ◽  
John Herbert
Keyword(s):  
Electrostatic Interactions ◽  
Mechanical Energy ◽  
Intermolecular Forces ◽  
Protein Crystal ◽  
Energy Decomposition Analysis ◽  
Quantum Mechanical ◽  
Electrostatic Repulsion ◽  
Pi Stacking ◽  
Intermolecular Distances ◽  
Pi Interactions

The nature of pi-pi interactions has long been debated. The term "pi-stacking" is considered by some to be a misnomer, in part because overlapping pi-electron densities are thought to incur steric repulsion, and the physical origins of the widely-encountered "slip-stacked" motif have variously been attributed to either sterics or electrostatics, in competition with dispersion. Here, we use quantum-mechanical energy decomposition analysis to investigate pi-pi interactions in supramolecular complexes of polycyclic aromatic hydrocarbons, ranging in size up to realistic models of graphene, and for comparison we perform the same analysis on stacked complexes of polycyclic <i>saturated</i> hydrocarbons, which are cyclohexane-based analogues of graphane. Our results help to explain the short-range structure of liquid hydrocarbons that is inferred from neutron scattering, trends in melting-point data, the interlayer separation of graphene sheets, and finally band gaps and observation of molecular plasmons in graphene nanoribbons. Analysis of intermolecular forces demonstrates that aromatic pi-pi interactions constitute a unique and fundamentally quantum-mechanical form of non-bonded interaction. Not only do stacked pi-pi architectures enhance dispersion, but quadrupolar electrostatic interactions that may be repulsive at long range are rendered attractive at the intermolecular distances that characterize pi-stacking, as a result of charge penetration effects. The planar geometries of aromatic sp<sup>2</sup> carbon networks lead to attractive interactions that are "served up on a molecular pizza peel", and adoption of slip-stacked geometries minimizes steric (rather than electrostatic) repulsion. The slip-stacked motif therefore emerges not as a defect induced by electrostatic repulsion but rather as a natural outcome of a conformation landscape that is dominated by van der Waals interactions (dispersion plus Pauli repulsion), and is therefore fundamentally quantum-mechanical in its origins. This reinterpretation of the forces responsible for pi-stacking has important implications for the manner in which non-bonded interactions are modeled using classical force fields, and for rationalizing the prevalence of the slip-stacked pi-pi motif in protein crystal structures.<br><br>

scholarly journals Reinterpreting π-Stacking

2020 ◽  
Author(s):  
Kevin Carter-Fenk ◽  
John Herbert
Keyword(s):  
Electrostatic Interactions ◽  
Mechanical Energy ◽  
Intermolecular Forces ◽  
Protein Crystal ◽  
Energy Decomposition Analysis ◽  
Quantum Mechanical ◽  
Electrostatic Repulsion ◽  
Pi Stacking ◽  
Intermolecular Distances ◽  
Pi Interactions

The nature of pi-pi interactions has long been debated. The term "pi-stacking" is considered by some to be a misnomer, in part because overlapping pi-electron densities are thought to incur steric repulsion, and the physical origins of the widely-encountered "slip-stacked" motif have variously been attributed to either sterics or electrostatics, in competition with dispersion. Here, we use quantum-mechanical energy decomposition analysis to investigate pi-pi interactions in supramolecular complexes of polycyclic aromatic hydrocarbons, ranging in size up to realistic models of graphene, and for comparison we perform the same analysis on stacked complexes of polycyclic <i>saturated</i> hydrocarbons, which are cyclohexane-based analogues of graphane. Our results help to explain the short-range structure of liquid hydrocarbons that is inferred from neutron scattering, trends in melting-point data, the interlayer separation of graphene sheets, and finally band gaps and observation of molecular plasmons in graphene nanoribbons. Analysis of intermolecular forces demonstrates that aromatic pi-pi interactions constitute a unique and fundamentally quantum-mechanical form of non-bonded interaction. Not only do stacked pi-pi architectures enhance dispersion, but quadrupolar electrostatic interactions that may be repulsive at long range are rendered attractive at the intermolecular distances that characterize pi-stacking, as a result of charge penetration effects. The planar geometries of aromatic sp<sup>2</sup> carbon networks lead to attractive interactions that are "served up on a molecular pizza peel", and adoption of slip-stacked geometries minimizes steric (rather than electrostatic) repulsion. The slip-stacked motif therefore emerges not as a defect induced by electrostatic repulsion but rather as a natural outcome of a conformation landscape that is dominated by van der Waals interactions (dispersion plus Pauli repulsion), and is therefore fundamentally quantum-mechanical in its origins. This reinterpretation of the forces responsible for pi-stacking has important implications for the manner in which non-bonded interactions are modeled using classical force fields, and for rationalizing the prevalence of the slip-stacked pi-pi motif in protein crystal structures.<br><br>

200kv superconducting cryo electron microscope

1987 ◽  
Vol 45 ◽  
pp. 642-643
Author(s):  
M. Iwatsuki ◽  
Y. Kokubo ◽  
Y. Harada ◽  
J. Lehman
Keyword(s):  
Electron Microscope ◽  
Structure Analysis ◽  
Organic Materials ◽  
Strong Interactions ◽  
Specimen Preparation ◽  
Great Effort ◽  
Electron Microscopic ◽  
Crystal Fields ◽  
Special Skill ◽  
Long Time

In recent years, the electron microscope has been significantly improved in resolution and we can obtain routinely atomic-level high resolution images without any special skill. With this improvement, the structure analysis of organic materials has become one of the interesting targets in the biological and polymer crystal fields.Up to now, X-ray structure analysis has been mainly used for such materials. With this method, however, great effort and a long time are required for specimen preparation because of the need for larger crystals. This method can analyze average crystal structure but is insufficient for interpreting it on the atomic or molecular level. The electron microscopic method for organic materials has not only the advantage of specimen preparation but also the capability of providing various information from extremely small specimen regions, using strong interactions between electrons and the substance. On the other hand, however, this strong interaction has a big disadvantage in high radiation damage.

New form of Transmission Cross Coefficient for High-Resolution Imaging

1990 ◽  
Vol 48 (1) ◽  
pp. 60-61
Author(s):  
Kazuo Ishizuka
Keyword(s):  
Electron Microscope ◽  
High Resolution ◽  
Transmission Function ◽  
Incident Beam ◽  
Optical Microscope ◽  
Strong Interactions ◽  
Small Range ◽  
Specimen Thickness ◽  
Beam Direction ◽  
Diffracted Waves

It is well known that taking into account spacial and temporal coherency of illumination as well as the wave aberration is important to interpret an image of a high-resolution electron microscope (HREM). This occues, because coherency of incident electrons restricts transmission of image information. Due to its large spherical and chromatic aberrations, the electron microscope requires higher coherency than the optical microscope. On an application of HREM for a strong scattering object, we have to estimate the contribution of the interference between the diffracted waves on an image formation. The contribution of each pair of diffracted waves may be properly represented by the transmission cross coefficients (TCC) between these waves. In this report, we will show an improved form of the TCC including second order derivatives, and compare it with the first order TCC.In the electron microscope the specimen is illuminated by quasi monochromatic electrons having a small range of illumination directions. Thus, the image intensity for each energy and each incident direction should be summed to give an intensity to be observed. However, this is a time consuming process, if the ranges of incident energy and/or illumination direction are large. To avoid this difficulty, we can use the TCC by assuming that a transmission function of the specimen does not depend on the incident beam direction. This is not always true, because dynamical scattering is important owing to strong interactions of electrons with the specimen. However, in the case of HREM, both the specimen thickness and the illumination angle should be small. Therefore we may neglect the dependency of the transmission function on the incident beam direction.

Depletion of coating color components in the blade coating process circulation

TAPPI Journal ◽  
2011 ◽  
Vol 10 (9) ◽  
pp. 17-23 ◽  
Author(s):  
ANNE RUTANEN ◽  
MARTTI TOIVAKKA
Keyword(s):  
Fine Particles ◽  
Particle Density ◽  
Stable Process ◽  
Size Fraction ◽  
Color Stability ◽  
Strong Interactions ◽  
Coating Process ◽  
Size Segregation ◽  
Coating Color ◽  
Average Size

Coating color stability, as defined by changes in its solid particle fraction, is important for runnability, quality, and costs of a paper coating operation. This study sought to determine whether the size or density of particles is important in size segregation in a pigment coating process. We used a laboratory coater to study changes in coating color composition during coating operations. The results suggest that size segregation occurs for high and low density particles. Regardless of the particle density, the fine particle size fraction (<0.2 μm) was the most prone for depletion, causing an increase in the average size of the particles. Strong interactions between the fine particles and other components also were associated with a low depletion tendency of fine particles. A stable process and improved efficiency of fine particles and binders can be achieved by controlling the depletion of fine particles.

Strong interactions at very high energy

1964 ◽  
Vol 82 (1) ◽  
pp. 3-81 ◽  
Author(s):  
Evgenii L. Feinberg ◽  
Dmitrii S. Chernavskii
Keyword(s):  
High Energy ◽  
Strong Interactions ◽  
Very High Energy ◽  
Very High

The intermolecular anthracene-transfer in a regiospecific antipodal C60 difunctionalization

2020 ◽  
Author(s):  
Radu Talmazan ◽  
Klaus R. Liedl ◽  
Bernhard Kräutler ◽  
Maren Podewitz
Keyword(s):  
Noncovalent Interactions ◽  
Interaction Model ◽  
Alder Reaction ◽  
Diels Alder ◽  
Stacking Interactions ◽  
Pi Stacking ◽  
Diels Alder Reaction ◽  
Double Decker ◽  
Anthracene Molecule ◽  
New Strategies

We analyze the mechanism of the topochemically controlled difunctionalization of C60 and anthracene, where an anthracene molecule is transferred from one C60 monoadduct to another one under exclusive formation of equal amounts of C60 and the difficult to make antipodal C60 bisadduct. Our herein disclosed dispersion corrected DFT studies show the anthracene transfer to take place in a synchronous retro Diels-Alder/Diels-Alder reaction: an anthracene molecule dissociates from one fullerene under formation of an intermediate, while already undergoing stabilizing interactions with both neighboring fullerenes, facilitating the reaction kinetically. In the intermediate, a planar anthracene molecule is sandwiched between two neighboring fullerenes and forms equally strong "double-decker" type pi-pi stacking interactions with both of these fullerenes. Analysis with the distorsion interaction model shows that the anthracene unit of the intermediate is almost planar with minimal distorsions. This analysis sheds light on the existence of noncovalent interactions engaging both faces of a planar polyunsaturated ring and two convex fullerene surfaces in an unprecedented 'inverted sandwich' structure. Hence, it sheds light on new strategies to design functional fullerene based materials.<br>

Stereospecific 1,3-H Transfer of Indenols Proceeds via Persistent Ion-Pairs Anchored By NH···Pi Interactions

2018 ◽  
Author(s):  
David Ascough ◽  
Fernanda Duarte ◽  
Robert Paton
Keyword(s):  
Computational Analysis ◽  
Ion Pairs ◽  
Ion Pair ◽  
Hydrogen Atom Transfer ◽  
Polar Solvents ◽  
Chirality Transfer ◽  
Activation Barriers ◽  
Sense And Avoid ◽  
Phase Dynamics ◽  
Pi Interactions

The base-catalyzed rearrangement of arylindenols is a rare example of a suprafacial [1,3]-hydrogen atom transfer. The mechanism has been proposed to proceed via sequential [1,5]-sigmatropic shifts, which occur in a selective sense and avoid an achiral intermediate. A computational analysis using quantum chemistry casts serious doubt on these suggestions: these pathways have enormous activation barriers and in constrast to what is observed experimentally, they overwhelmingly favor a racemic product. Instead we propose that a suprafacial [1,3]-prototopic shift occurs in a two-step deprotonation/reprotonation sequence. This mechanism is favored by 15 kcal mol<sup>-1</sup> over that previously proposed. Most importantly, this is also consistent with stereospecificity since reprotonation occurs rapidly on the same p-face. We have used explicitly-solvated molecular dynamics studies to study the persistence and condensed-phase dynamics of the intermediate ion-pair formed in this reaction. Chirality transfer is the result of a particularly resilient contact ion-pair, held together by electrostatic attraction and a critical NH···p interaction which ensures that this species has an appreciable lifetime even in polar solvents such as DMSO and MeOH.

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