Charge-induced Dipole Interaction Research Articles

Calculation of liquidus in eutectic alkali halide mixtures using thermodynamic perturbation theory

A statistical-thermodynamic model that makes it possible to describe with good accuracy phase equilibria between melt and crystal in binary alkali halide mixtures with common cations and anions is proposed. This model is based on the thermodynamic perturbation theory, which takes into account the charge-dipole contribution to the interionic interaction of binary molten salts using a multicomponent mixture of charged hard spheres as a reference system. Specific expressions for chemical potentials, taking into account the charge-induced dipole interaction in the molten phase, are presented within the developed approach. Considering binary eutectic mixtures NaF–NaCl, CsF–CsCl, NaF–CsF, and NaCl–CsCl as an example, the liquidus curves obtained in two series of calculations are shown: with the equation of state and without it. The discrepancies between the calculated and experimental data on the position of eutectic equilibrium for most of the considered mixtures do not exceed about 10 percent on the temperature scale and 5 percent on the composition when using only the tabulated values of ionic radii and polarizabilities without any adjustment.

Large scale purification in semiconductors using Rydberg excitons

Improving the quantum coherence of solid-state systems is a decisive factor in realizing solid-state quantum technologies. The key to optimize quantum coherence lies in reducing the detrimental influence of noise sources such as spin noise and charge noise. Here we demonstrate that we can utilize highly-excited Rydberg excitons to neutralize charged impurities in the semiconductor Cuprous Oxide - an effect we call purification. Purification reduces detrimental electrical stray fields drastically. We observe that the absorption of the purified crystal increases by up to 25% and that the purification effect is long-lived and may persist for hundreds of microseconds or even longer. We investigate the interaction between Rydberg excitons and impurities and find that it is long-ranged and based on charge-induced dipole interactions. Using a time-resolved pump-probe technique, we can discriminate purification from Rydberg blockade, which has been a long-standing goal in excitonic Rydberg systems.

Electronic states, spectroscopic properties, electronic transitions, and bonding in ScH2+: A thermodynamic stable transition metal-hydrogen dication

Eight bound singlet and triplet electronic states of the diatomic dication ScH2+ are characterized theoretically at the SA-CASSCF/icMRCI/aug-cc-pV5Z level of theory by the construction of potential energy curves, and the evaluation of spectroscopic parameters. The states dissociating into the first channel are all thermodynamically stable. For the ground state, covalent bonding plays a relevant role in the stabilization of the molecule; for the other states, bonding results mainly from electrostatic charge-induced dipole interaction. Dipole moment (relative to the center of mass) functions and vibrationally averaged dipole moments quantify the polarity of the molecule. After evaluating transition moment functions, transition probabilities for spontaneous emission for selected pair of states are estimated by the Einstein Av´,v´´ coefficients and the stronger transitions identified; radiative lifetimes are also reported. Not yet known experimentally, this work is expected to motivate experimental investigations of transition metal-monohydrides diatomic dications.

Characterizing electronic states in metal-rare gas diatomic dications: The cases of VAr2+ and VKr2+

Six low-lying bound quartet electronic states of the diatomic dications VAr2+ and VKr2+ are characterized theoretically at the SA-CASSCF/icMRCI/aug-cc-pV5Z level of theory by the construction of potential energy curves, and the evaluation of spectroscopic parameters. These molecules were found to be thermodynamically stable, where binding arises from purely electrostatic charge-induced dipole interaction; they are more strongly bound than the corresponding monocations. Their polarity is described by dipole moment functions and vibrationally averaged dipole moments. Transition probabilities for spontaneous emission for selected pair of states are estimated by the Einstein Av′v′′ coefficients and the stronger transitions identified; radiative lifetimes are also reported. Not yet known experimentally, this work is expected to motivate further experimental investigations of transition metal-rare-gas diatomic dications.

Noncovalent chemistry of xenon opens the door for anesthetic xenon recovery using Bio-MOFs.

Designing an inexpensive and highly efficient recovery process for xenon (Xe) is gaining importance in the development of sustainable applications. Using metal organic frameworks (MOFs) for separating Xe from anesthetic gas mixtures has been a recent topic studied rarely and superficially in the literature. We theoretically investigated Xe recovery performances of 43 biological MOFs (Bio-MOFs) formed by biocompatible metal cations and biological endogenous linkers. Xe uptakes and Xe permeabilities in its binary mixtures with CO2, O2, and N2 were investigated by applying Grand Canonical Monte Carlo and Molecular Dynamics simulations. Materials with metalloporphyrin, hexacarboxylate, triazine, or pyrazole ligands, dimetallic paddlewheel units, relatively large pore sizes (PLD > 5 Å and LCD > 10 Å), large void fractions (≈0.8), and large surface areas (>2900 m2 g-1) have been determined as top performing Bio-MOFs for Xe recovery. By applying Density Functional Theory simulations and generating electron density difference maps, we determined that Xe-host interactions in the top performing Bio-MOFs are maximized mainly due to noncovalent interactions of Xe, such as charge-induced dipole and aerogen-π interactions. Polarized Xe atoms in the vicinity of cations/anions as well as π systems are fingerprints of enhanced guest-host interactions. Our results show examples of rarely studied aerogen interactions that play a critical role in selective adsorption of Xe in nanoporous materials.

Heat capacity of molten alkali halides

Experimental data on the heat capacities of molten alkali halides near their melting points are analyzed depending on cation–anion composition. The isochoric heat capacities of all 20 liquid alkali halides were calculated using thermodynamic perturbation theory (TPT) based on a reference system of charged hard spheres + charge-induced dipole contribution to pairwise ionic interaction. Changes in the heat capacity depending on the ratio of ionic radii and polarizabilities are identified and described. On this basis, recommended heat capacity values are selected from the various experimental data. It is shown that the reduced isochoric heat capacity (CV/kB) should increase with a mismatch in the cation and anion radii as an even function with a minimum. Charge-induced dipole interactions lead to a breaking of the specific Coulomb symmetry, resulting in a more significant increase in the heat capacity for salts containing the smallest cations, as well as the anions with largest size and polarizability.

Characterizing electronic states and spectra in transition metal-rare gas diatomic cations: The cases of VAr+ and VKr+

Nine low-lying quintet electronic states of the cations VAr+ and VKr+ are characterized theoretically at the SA-CASSCF/icMRCI/aug-cc-pV5Z level of theory by the construction of potential energy curves and the determination of spectroscopic parameters. The polarity of the molecules is described by dipole moment functions and vibrationally averaged dipole moments. Transition probabilities for spontaneous emission for selected states are estimated by the Einstein Av´,v´´ coefficients and the stronger transitions identified; radiative lifetimes are also reported. For the photoabsorption process, the spectrum is modelled for the bands of the G 5Π – X 5Σ+ system of each species for which experimental photodissociation results are available in the literature. Not known experimentally, the intensity distribution is expected to help elucidate the assumed vibrational numbering of the upper state, and together with the overall electronic description and spectroscopic parameters motivate further experimental investigations of transition metal-rare-gas cations. Binding arises from purely electrostatic charge-induced dipole interaction.

Experimental study of the proton-transfer reaction C + H2+ → CH+ + H and its isotopic variant (D2+).

We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of Er ∼ 0.01-10 eV. We used photodetachment of C- to produce a pure beam of atomic C in the ground electronic 3P term, with statistically populated fine-structure levels. The H2+ and D2+ were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH2+ electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 14A' and 14A'' states of CH2+via the reaction C(3P) + H2+(2Σ+g) → CH+(3Π) + H(2S). We also hypothesize that at low collision energies only H2+(v ≤ 2) and D2+(v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ⪅0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30-50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction.

Comparing Empty and Filled Fullerene Cages with High-Resolution Trapped Ion Mobility Spectrometry.

We have used trapped ion mobility spectrometry (TIMS) to obtain highly accurate experimental collision cross sections (CCS) for the fullerene C80- and the endohedral metallofullerenes La2@C80-, Sc3N@C80-, and Er3N@C80- in molecular nitrogen. The CCS values of the endohedral fullerenes are 0.2% larger than that of the empty cage. Using a combination of density functional theory and trajectory calculations, we were able to reproduce these experimental findings theoretically. Two effects are discussed that contribute to the CCS differences: (i) a small increase in fullerene cage size upon endohedral doping and (ii) charge transfer from the encapsulated moieties to the cage thus increasing the attractive charge-induced dipole interaction between the (endohedral) fullerene ion and the nitrogen bath gas molecules.

Assessing the Performance of the Nonbonded Mg2+ Models in a Two-Metal-Dependent Ribonuclease.

Magnesium ions (Mg2+), abundant in living cells, are essential for biomolecular structure, dynamics, and function. The biological importance of Mg2+ has motivated continuous development and improvement of various Mg2+ models for molecular dynamics (MD) simulations during the last decades. There are four types of nonbonded Mg2+ models: the point charge models based on a 12-6 or 12-6-4 type Lennard-Jones (LJ) potential, and the multisite models based on a 12-6 or 12-6-4 LJ potential. Here, we systematically assessed the performance of these four types of nonbonded Mg2+ models (21 models in total) in terms of maintaining a challenging intermediate state configuration captured in the structure of a prototypical two-metal-ion RNase H complex with an RNA/DNA hybrid. Our data demonstrate that the 12-6-4 multisite models, which account for charge-induced dipole interactions, perform the best in reproducing all the unique coordination modes in this intermediate state and maintaining the correct carboxylate denticity. Our benchmark work provides a useful guideline for MD simulations and structural refinement of Mg2+-containing biomolecular systems.

Unprecedented Enhancement of Noble Gas-Noble Metal Bonding in NgAu3+ (Ng = Ar, Kr, and Xe) Ion through Hydrogen Doping.

Behavior of gold as hydrogen in certain gold compounds and a very recent experimental report on the noble gas-noble metal interaction in Ar complexes of mixed Au-Ag trimers have motivated us to investigate the effect of hydrogen doping on the Ng-Au (Ng = Ar, Kr, and Xe) bonding through various ab initio based techniques. The calculated results show considerable strengthening of the Ng-Au bond in terms of bond length, bond energy, stretching vibrational frequency, and force constant. Particularly, an exceptional enhancement of Ar-Au bonding strength has been observed in ArAuH2+ species as compared to that in ArAu3+ system, as revealed from the CCSD(T) calculated Ar-Au bond energy value of 32 and 72 kJ mol-1 for ArAu3+ and ArAuH2+, respectively. In the calculated IR spectra, the Ar-Au stretching frequency is blue-shifted by 65% in going from ArAu3+ to ArAuH2+ species. Similar trends have been obtained in the case of all Ar, Kr, and Xe complexes with Ag and Cu trimers. Among all the NgM3-kHk+ complexes (where k = 0-2), the strongest binding in NgMH2+ complex is attributed to significant enhancement in the covalent characteristics of the Ng-M bond and considerable increase in charge-induced dipole interaction, as shown from the topological analysis.

Intact Four-atom Organic Tetracation Stabilized by Charge Localization in the Gas Phase.

Several features distinguish intact multiply charged molecular cations (MMCs) from other species such as monocations and polycations: high potential energy, high electron affinity, a high density of electronic states with various spin multiplicities, and charge-dependent reactions. However, repulsive Coulombic interactions make MMCs quite unstable, and hence small organic MMCs are currently not readily available. Herein, we report that the isolated four-atom molecule diiodoacetylene survives after the removal of four electrons via tunneling. We show that the tetracation remains metastable towards dissociation because of the localization (91-95 %) of the positive charges on the terminal iodine atoms, ensuring minimum Coulomb repulsion between adjacent atoms as well as maximum charge-induced attractive dipole interactions between iodine and carbon. Our approach making use of iodines as the positively charged sites enables small organic MMCs to remain intact.

On the structure, masses and thermodynamics of the W[formula omitted] bosons

Using Newton’s universal gravitational law but with gravitational instead of rest masses, and the de Broglie wavelength equation, we show by computing from first principles their mass that the W+ and W− bosons correspond to relativistic e+−νe and e−−νe rotating pairs. This appears consistent with the fact that W+ and W− bosons are known to decay to e+−νe and e−−νe couples, respectively.The model contains no adjustable parameters and in addition to the computed masses, potential energies, decomposition temperatures, and lifetimes, are in good agreement with experiment. This agreement can be further improved upon considering, in addition to the relativistic gravitational force, the Coulombic charge-induced dipole interactions between the charged components (positrons or electrons) and the polarizable neutrinos.

Alkali and alkaline-earth atom-decorated B38 fullerenes and their potential for hydrogen storage

The structural and electronic properties of alkali and alkaline-earth metal (Li, Na, K, Mg, and Ca) atom-decorated B38 fullerene, as well as their potential for hydrogen storage, are studied using all-electron density functional theory. The metal atoms favor face-capping on top of the center of hexagonal holes of fullerene. Large binding energy prevents alkali and alkaline-earth atoms from clustering on the surface of B38. Large amounts of positive charges are found on Na, K, and Ca atoms. We find that calcium-coated B38 is the best candidate for hydrogen storage, with moderate adsorption energy of H2. One Ca atom can adsorb up to five H2 molecules, resulting in 20 H2 molecules that can be stored in Ca4–B38 with an average binding energy intermediate of 0.075 and 0.240 eV/H2. The hydrogen storage capacity reaches up to 6.47 wt.%. Charge-induced dipole interaction is responsible for the high hydrogen storage capacity of Ca4–B38.

Charge-induced dipole vs. relativistically enhanced covalent interactions in Ar-tagged Au-Ag tetramers and pentamers.

Vibrational spectra of Au(n)Ag(m)(+)⋅Ar(k) (n + m = 4, 5; k = 1-4) clusters are determined by far-infrared resonant multiple photon dissociation spectroscopy in the range ν̃=100-250 cm(-1). The experimental spectra are assigned using density functional theory for geometries obtained by the Birmingham cluster genetic algorithm. Putative global minimum candidates of the Ar complexes are generated by adding Ar atoms to the Au(n)Ag(m)(+) low energy isomers and subsequent local optimization. Differential Ar binding energies indicate exceptionally strong Au-Ar bonds in Au-rich clusters, leading to fundamental changes to the IR spectra. The stronger Ar binding is attributed to a relativistically enhanced covalent character of the Au-Ar bond, while in Au-rich species charge-induced dipole interactions overcompensate the relativistic affinity to Au. Moreover, not only the absolute composition but also the topologies are essential in the description of Ar binding to a certain cluster.

Modeling of cell adhesion and deformation mediated by receptor-ligand interactions.

The current work is devoted to studying adhesion and deformation of biological cells mediated by receptors and ligands in order to enhance the existing models. Due to the sufficient in-plane continuity and fluidity of the phospholipid molecules, an isotropic continuum fluid membrane is proposed for modeling the cell membrane. The developed constitutive model accounts for the influence of the presence of receptors on the deformation and adhesion of the cell membrane through the introduction of spontaneous area dilation. Motivated by physics, a nonlinear receptor-ligand binding force is introduced based on charge-induced dipole interaction. Diffusion of the receptors on the membrane is governed by the receptor-ligand interaction via Fick's Law and receptor-ligand interaction. The developed model is then applied to study the deformation and adhesion of a biological cell. The proposed model is used to study the role of the material, binding, spontaneous area dilation and environmental properties on the deformation and adhesion of the cell.

Solvation of Intrinsic Positive Charge in Superfluid Helium

On the basis of electronic structure calculations, the structure of intrinsic positive charge solvated in superfluid helium is identified as triatomic He3(+) ion, which is bound to the surrounding ground state helium atoms through the charge–charge induced dipole interaction in a pairwise additive manner. Bosonic density functional theory calculations show that this ion forms the well-known Atkins’ snowball solvation structure where the first rigid helium shell is effectively disconnected from the rest of the liquid. Evaluation of the total energy vs helium droplet size N shows distinct regions related to the completion of solvent shells near N = 16 and N = 47. These regions can be assigned to magic numbers observed in positively charged helium droplets appearing at N = 15 and in the range between 20 and 50 helium atoms. The calculated added mass for the positive ion in bulk superfluid helium (18 mHe) is much smaller than the previous experiments suggest (30–40 mHe), indicating that there may be yet some unidentified additional factor contributing to the measured effective mass. Both previous experiments and the present calculations agree on the effective mass of the negative charge (240–250 mHe). The main difference between the solvated negative and positive charges in liquid helium is that the latter forms a chemically bound triatomic molecule surrounded by highly inhomogeneous liquid structure whereas the former remains as a separated charge with a smoothly varying liquid density around it.

Taking into Account the Ion-induced Dipole Interaction in the Nonbonded Model of Ions.

Metal ions exist in almost half of the proteins in the protein databank and they serve as structural, electron-transfer and catalytic elements in the metabolic processes of organisms. Molecular Dynamics (MD) simulation is a powerful tool that provides information about biomolecular systems at the atomic level. Coupled with the growth in computing power, algorithms like the Particle Mesh Ewald (PME) method have become the accepted standard when dealing with long-range interactions in MD simulations. The nonbonded model of metal ions consists of an electrostatic plus 12-6 Lennard Jones (LJ) potential and is used largely because of its speed relative to more accurate models. In previous work we found that ideal parameters do not exist that reproduce several experimental properties for M(II) ions simultaneously using the nonbonded model coupled with the PME method due to the underestimation of metal ion-ligand interactions. Via a consideration of the nature of the nonbonded model, we proposed that the observed error largely arises from overlooking charge-induced dipole interactions. The electrostatic plus 12-6 LJ potential model works reasonably well for neutral systems but does struggle with more highly charged systems. In the present work we designed and parameterized a new nonbonded model for metal ions by adding a 1/r4 term to the 12-6 model. We call it the 12-6-4 LJ-type nonbonded model due to its mathematical construction. Parameters were determined for 16 +2 metal ions for the TIP3P, SPC/E and TIP4PEW water models. The final parameters reproduce the experimental hydration free energies (HFE), ion-oxygen distances (IOD) in the first solvation shell and coordination numbers (CN) accurately for the metal ions investigated. Preliminary tests on MgCl2 at different concentrations in aqueous solution and Mg2+--nucleic acid systems show reasonable results suggesting that the present parameters can work in mixed systems. The 12-6-4 LJ-type nonbonded model is readily adopted into standard force fields like AMBER, CHARMM and OPLS-AA with only a modest computational overhead. The new nonbonded model doesn't consider charge-transfer effects explicitly and, hence, may not suitable for the simulation of systems where charge-transfer effects play a decisive role.

Hydrogen storage by physisorption on dodecahydro-closo-dodecaboranes

Hydrogen physisorption on dodecahydro-closo-dodecaborane units is studied using ab initio quantum chemical calculations based on Møller-Plesset perturbation theory. After adding zero-point energy corrections, the adsorption energy due to the charge-quadrupole and the charge-induced dipole interaction is somewhat larger than the more common dispersion interaction with spacer molecules in molecular framework compounds. Furthermore, the energy landscape on the surface of the near-spherical B12H12(2-) permits considerable residual dynamics with corresponding configurational entropy that releases partly the requirements on the magnitude of the adsorption energy. If it can be made fully accessible in an open architecture the system promises an enormous storage capacity. An experimental test for Cs2B12H12 dispersed in the cages of a dealuminated faujasite zeolite amends the theoretical study.

Synthesis of zeolite-casted microporous carbons and their hydrogen storage capacity

Zeolite-casted microporous carbons (ZMiPCs) were synthesized using the replica casting method. The ZMiPC were also treated chemically by H3PO4 (A-ZMiPC) or KOH (B-ZMiPC) impregnation, to investigate the effect of the acceptor–donor interaction on the hydrogen storage behaviors. The presence of functional groups of the modified ZMiPC surfaces was confirmed by X-ray photoelectron spectroscopy. The total acidity of the carbon surfaces was determined using the Boehm titration method. The microstructure was characterized by X-ray diffraction. The N2/77K adsorption/desorption isotherms were analyzed to characterize specific surface area, pore volume, and pore size distribution of the samples. The capacity of hydrogen adsorption was evaluated using a pressure-composition-temperature apparatus at 298K/100bar. From these results, the specific surface areas and micropore volume of ZMiPC increased more than two fold compared to the zeolite template. Meanwhile, the textural properties of A-ZMiPC and B-ZMiPC were decreased by the chemical treatments. Consequently, the largest hydrogen storage was obtained on A-ZMiPC, even though their textural properties had decreased, due to a charge induced dipole interaction between the modified carbon surface and hydrogen molecules.