Search results for "London dispersion force"

A three-coordinate iron–silylene complex stabilized by ligand–ligand dispersion forces

2016

The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(II) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding.

Vacuum-ultraviolet absorption of interstitial O2 and H2O molecules in SiO2 glass

2006

Abstract Vacuum-ultraviolet (VUV) absorption of O 2 and H 2 O molecules incorporated in interstitial voids in SiO 2 glass by thermal annealings was examined. Interactions of the interstitial molecules with the surrounding SiO 2 glass network lead to a redshift of the VUV absorption band of interstitial O 2 , while a blueshift of that of interstitial H 2 O, both accompanied by an increase in the intensity of the absorption bands. The Coulomb repulsion, London dispersion, and hydrogen bonding are the main interactions responsible for the modification of the VUV absorption bands.

van der Waals interactions between excited atoms in generic environments

2015

We consider the the van der Waals force involving excited atoms in general environments, constituted by magnetodielectric bodies. We develop a dynamical approach studying the dynamics of the atoms and the field, mutually coupled. When only one atom is excited, our dynamical theory suggests that for large distances the van der Waals force acting on the ground-state atom is monotonic, while the force acting in the excited atom is spatially oscillating. We show how this latter force can be related to the known oscillating Casimir--Polder force on an excited atom near a (ground-state) body. Our force also reveals a population-induced dynamics: for times much larger that the atomic lifetime the …

2020

The reaction of the copper(I) β-diketiminate copper complex {(Cu(BDIMes))2(μ-C6H6)} (BDIMes = N,N'-bis(2,4,6-trimethylphenyl)pentane-2,4-diiminate) with the low-valent group 13 metal β-diketiminates M(BDIDip) (M = Al or Ga; BDIDip = N,N'-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate) in toluene afforded the complexes {(BDIMes)CuAl(BDIDip)} and {(BDIMes)CuGa(BDIDip)}. These feature unsupported copper-aluminum or copper-gallium bonds with short metal-metal distances, Cu-Al = 2.3010(6) A and Cu-Ga = 2.2916(5) A. Density functional theory (DFT) calculations showed that approximately half of the calculated association enthalpies can be attributed to London dispersion forces.

Dispersion Interaction between Two Hydrogen Atoms in a Static Electric Field

2019

We consider the dispersion interaction between two ground-state hydrogen atoms, interacting with the quantum electromagnetic field in the vacuum state, in the presence of an external static electric field, both in the nonretarded and in the retarded Casimir-Polder regime. We show that the presence of the external field strongly modifies the dispersion interaction between the atoms, changing its space dependence. Moreover, we find that, for specific geometrical configurations of the two atoms with respect to the external field and/or the relative orientation of the fields acting on the two atoms, it is possible to change the character of the dispersion force, turning it from attractive to re…

Carbon nanorings: A challenge to theoretical chemistry

2006

High-level quantum-chemical methods show that the binding in the inclusion complex of hexamethylbenzene (HMB) in 6-cycloparaphenilacetylene (6-CPPA) cannot be explained only in terms of electrostatic interactions - caused by the polarization associated to curved π-conjugated systems - and the inclusion of dispersion forces is definitely needed. The theoretical description of van der Waals interactions is notoriously complicated and in fact some DFT methods cannot even predict the existence of the relatively small supramolecular nanoring studied here. However, ab initio MP2 calculations agree with experimental data and show that, in the considered complex, the HMB fragment is placed at the …

Discriminating short-range from van der Waals forces using total force data in noncontact atomic force microscopy

2014

Noncontact atomic force microscopy (NC-AFM) features the measurement of forces with highest spatial resolution and sensitivity, resolving forces of the order of pico-Newtons with submolecular resolution. However, the measured total force is a mixture composed of various interactions. While some interactions such as electrostatic or magnetic forces can be excluded by a careful design of the experiment, the subtraction of van der Waals forces, which mainly originate from London dispersion interactions between the macroscopic tip shank and the bulk sample, remains a challenge. We present the determination of the inherently present van der Waals forces in total interaction force data from fitti…

Intermolecular interaction energies and magnetic properties of spin-isolated multinuclear CuII complexes

2020

Dinuclear CuII complexes with 3,5-dinitrobenzoates and 2,2′-bipyridine (2) or 1,10-phenanthroline (3) were synthesized and characterized. A complete energy framework analysis using the HF/3-21G energy model was performed which found that dispersion forces and C—H...O interactions are responsible for the crystal structure features. The magnetic properties of the complexes show a weak magnetic exchange between spins, resulting in low exchange constants of −2.72 (1) cm−1 and −1.10 (1) cm−1 for complexes (2) and (3), respectively. This results from the low overlap between magnetic orbitals induced by 3,5-dinitrobenzoate bridges and the arrangement of the magnetic orbitals. Consequently, the din…

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-9…

2013

The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…

Energy interactions in amyloid-like fibrils from NNQQNY.

2014

We use large-scale MP2 calculations to analyze the interactions appearing in amyloid fibers, which are difficult to determine experimentally. To this end, dimers and trimers of the hexapeptide NNQQNY from the yeast prion-like protein Sup35 were considered as model systems. We studied the energy interactions present in the three levels of organization in which the formation of amyloid fibrils is structured. The structural changes in the hydrogen bonds were studied too. It was found that the most energetic process is the formation of the β-sheet, which is equally due to both hydrogen bonds and van der Waals interactions. The aromatic rings help stabilize these aggregates through stacking of t…