Attractive Dipole-dipole Interactions Research Articles

NO-Induced Reorganization of Porphyrin Arrays

We studied the interaction of a highly ordered array of Co-tetraphenylporphyrin (CoTPP) with NO on Ag(111) by in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. Upon NO exposure, the initially quadratically ordered CoTPP layer reorganizes, showing a wealth of highly ordered NO+CoTPP coadsorbate phases with increasing size of the unit cell, interpreted as due to attractive lateral dipole-dipole interactions between the two species. The findings not only suggest a novel approach to control the arrangement of adsorbed porphyrins in particular but also should generally be considered in the production of functional layers from large organic molecules under ambient conditions or after exposure to small electronegative molecules.

Collapse instability of solitons in the nonpolynomial Schrödinger equation with dipole–dipole interactions

A model of the Bose–Einstein condensate (BEC) of dipolar atoms, confined in a combination of a cigar-shaped trap and optical lattice acting in the axial direction, is studied in the framework of the one-dimensional (1D) nonpolynomial Schrödinger equation (NPSE) with additional terms describing long-range dipole–dipole (DD) interactions. The NPSE makes it possible to describe the collapse of localized modes, which was experimentally observed in the self-attractive BEC confined in tight traps, in the framework of the 1D description. We study the influence of the DD interactions on the dynamics of bright solitons, especially concerning their collapse-induced instability. Both attractive and repulsive contact and DD interactions are considered. The results are summarized in the form of stability/collapse diagrams in a respective parametric space. In particular, it is shown that the attractive DD interactions may prevent the collapse instability in the condensate with attractive contact interactions.

Solitons in quasi-one-dimensional Bose-Einstein condensates with competing dipolar and local interactions

We study families of one-dimensional matter-wave bright solitons supported by the competition of contact and dipole-dipole (DD) interactions of opposite signs. Soliton families are found, and their stability is investigated in the free space, and in the presence of an optical lattice (OL). Free-space solitons may exist with an arbitrarily weak local attraction if the strength of the DD repulsion is fixed. In the case of the DD attraction, solitons do not exist beyond a maximum value of the local-repulsion strength. In the system which includes the OL, a stability region for \textit{subfundamental solitons} (SFSs) is found in the second finite bandgap. For the existence of gap solitons (GSs) under the attractive DD interaction, the contact repulsion must be strong enough. In the opposite case of the DD repulsion, GSs exist if the contact attraction is not too strong. Collisions between solitons in the free space are studied too. In the case of the local attraction, they merge or pass through each other at small and large velocities, respectively. In the presence of the local repulsion, slowly moving solitons bounce from each other.

Dipolar Side Chain Control of Monolayer Morphology: Symmetrically Substituted 1,5-(Mono- and diether) Anthracenes at the Solution−HOPG Interface

Scanning tunneling microscopy (STM) is used to determine the 2-D unit cell parameters of monolayers self-assembled by twelve symmetrical, 1,5-bis(linear aliphatic ether side chain) anthracenes at the solution-graphite interface. The standard morphology assembled by 1,5-bis(alkyloxymethyl) anthracenes consists of single-lamella domains containing columns of anthracene cores alternating with columns of interdigitated, aliphatic side chains. Adjacent side chains within the aliphatic columns adsorb in antiparallel orientations. The terminal methyl (omega-position) of each side chain lies in registration with the 2-positions of its two neighboring chains ((omega <--> 2)-packing). Anthracenes with diether side chains can generate repulsive or attractive dipole-dipole interactions between proximate ethers of adjacent aliphatic chains. Anthracenes bearing even length side chains with oxygens at the 2- and omega-1 positions or at the 3- and omega-2 positions do not assemble (omega <--> 2)-packed monolayers. Repulsive dipolar interactions between ethers in adjacent side chains raise the energy of (omega <--> 2) morphologies. These "self-repulsive" side chains drive assembly of (omega <--> l)- or (omega <--> 3)-packed morphologies, which enjoy stabilizing dipolar interactions between ethers in adjacent side chains. In stark contrast, anthracenes bearing odd length diether side chains assemble (omega <--> 2)-packed morphologies, regardless of whether adjacent chains suffer zero, one, or two sets of proximate dipole-dipole repulsions. The intrinsic energy gap from (omega <--> 2)- to non-(omega <--> 2)-packed morphologies of odd length side chain anthracenes is, apparently, larger than for even length side chain anthracenes. Overall, the twelve compounds self-assemble seven different morphologies. Distinguishing morphologies, understanding polymorphism within the monolayers, and evaluating the morphological consequences of side chain dipolar interactions is facilitated by viewing the monolayers as assemblies of 1-D, molecular tapes.

Melting a frozen Rydberg gas with an attractive potential

We report clear evidence of the role of the attractive dipole-dipole interaction in Penning ionization of Rydberg atoms, leading to the formation of an ultracold plasma. Penning ionization of $np$ Rydberg cesium atoms does not occur for states with $nl42$, which have repulsive potentials, but it does occur for states of $n$ larger than 42, which have attractive potentials. Blackbody radiation is mostly responsible for the background and initial ionization, although ion--Rydberg-atom collisions and population transfer due to limited superradiance may have to be considered.

Attractive membrane domains control lateral diffusion

Lipid membranes play a fundamental role in vital cellular functions such as signal transduction. Many of these processes rely on lateral diffusion within the membrane, generally a complex fluid containing ordered microdomains. However, little attention has been paid to the alterations in transport dynamics of a diffusing species caused by long-range interactions with membrane domains. In this paper, we address the effect of such interactions on diffusive transport by studying lateral diffusion in a phase-separated Langmuir phospholipid monolayer via single-particle tracking. We find that attractive dipole-dipole interactions between condensed phase domains and diffusing probe beads lead to transient confinement at the phase boundaries, causing a transition from two- to one-dimensional diffusion. Using Brownian dynamics simulations, the long-term diffusion constant for such a system is found to have a sensitive, Boltzmann-like, dependence on the interaction strength. In addition, this interaction strength is shown to be a strong function of the ratio of domain to particle size. As similar interactions are expected in biological membranes, the modulation of diffusive transport dynamics by varying interaction strength and/or domain size may offer cells selective spatial and temporal control over signaling processes.

A thermodynamic study by laser-flash photolysis of plastocyanin and cytochrome c6 oxidation by photosystem I from the green alga Monoraphidium braunii.

Plastocyanin and cytochrome c6 from the green alga Monoraphidium braunii reduce the photo-oxidized algal photosystem I (PSI) reaction center chlorophyll (P700) with similar kinetics, as expected from their functional equivalence. The observed P700+ reduction rate constants show a non-linear dependence on metalloprotein concentration, which indicates a (minimal) two-step kinetic mechanism involving complex formation prior to electron transfer. The dependence of the observed rate constants on NaCl concentration suggests that the electrostatic interaction forces between the negatively charged donor proteins and PSI are repulsive at neutral pH and relatively low ionic strength (I), although attractive dipole-dipole interactions may play a role at higher ionic strengths. Activation parameters for P700+ reduction by cytochrome c6 and plastocyanin have been determined by studying the temperature dependence of the respective rate constants at varying ionic strength and pH. Changes in NaCl concentration and pH induce significant changes in the activation free energy of the overall reaction, even though the corresponding values for activation enthalpy and entropy undergo changes in opposite directions. Such a compensation effect between enthalpy and entropy is observed with both cytochrome c6 and plastocyanin. Protein concentration dependencies of the observed rate constants at different temperatures has allowed an estimate of the free energy change during complex association, as well as the activation parameters for electron transfer, according to a two-step kinetic model.

Attractive dipole-dipole interaction between charge carriers in highly polarizable crystals

A new carrier coupling mechanism is proposed promoting the increase of the superconductive transition temperature based on dipole-dipole interaction between off-center polarons in highly polarizable media. The supposition is discussed that such an attractive interaction can take place in YBa 2Cu 3O 7−δ where charge carriers are the holes moving along oxygen sites. We discuss also the role of localized oxygen holes in the creation of ferroelectric regions discovered in YBa 2Cu 3O 7−δ.

The decomposition of formic acid on Ni(100)

The decomposition of HCOOD was studied on Ni(100). Low temperature adsorption of HCOOD resulted in the desorption of D 2O, CO 2, CO, and H 2. The D 2O was evolved below room temperature. CO 2 and H 2 were evolved in coincident peaks at a temperature above that at which h 2 desorbed following H 2 adsorption and well above that for CO 2 desorption from CO 2 adsorption; CO desorbed primarily in a desorption limited step. The decomposition of formic acid on the clean surface was found to yield equal amounts of H 2, CO, and CO 2 within experimental error. The kinetics and mechanism of the decomposition of formic acid on Ni (110) and Ni(100) single crystal surfaces were compared. The reaction proceeded by the dehydration of formic acid to formic anhydride on both surfaces. The anhydride intermediate condensed into islands due to attractive dipole-dipole interactions. Within the islands the rate of the decomposition reaction to form CO 2 was given by: Rate = 6 × 10 15 exp{−[25,500 + ω( c c sat )]/RT} × c , where c is the local surface concentration, c sat is the saturation coverage for the particular crystal plane, and ω is the interaction potential. The interaction potential was determined to be 2.7 kcal/mole on Ni(110) and 1.4 kcal/mole on Ni(100); the difference observed was due to structural differences of the surfaces relating to the alignment of the dipole moments within the islands. These attractive interactions resulted in an autocatalytic reaction on Ni(110), whereas the interaction was not strong enough on Ni(100) to sustain the autocatalytic behavior. Formic acid decomposition oxidized the Ni(100) surface resulting in the formation of a stable surface oxide. The buildup of the oxide resulted in a change in the selectivity reducing the amount of CO formed. This trend indicated that on the oxide surface the decomposition proceeded via a formate intermediate as on Ni(110) O.