Corrections to the Casimir–Polder potential arising from electric octupole coupling

ABSTRACT

Molecular QED theory is employed to derive a generalised formula for the dispersion potential between two molecules with mixed electric multipole polarisability tensors of arbitrary order at each centre. This expression is used to readily extract the pair energy shift between an electric dipole polarisable molecule and a mixed electric dipole–octupole polarisable one, and that between two mixed electric dipole–octupole polarisable species. This is done to see whether these interaction energies give rise to higher-order corrections to the Casimir–Polder potential, as was found in the previously calculated case of the dispersion energy shift between an electric dipole polarisable molecule and an electric octupole polarisable one. Interestingly, for orientationally averaged species, both of the computed interaction energies are independent of the octupole weight-3 term, are retarded, and may be interpreted as higher-order corrections in the fine structure constant to the leading dipole–dipole dispersion potential.     

Field-induced self-assembly: does size matter?

ABSTRACT

Simulated external electric fields are applied to polarisable species containing either a monodisperse of bidisperse distribution of polarisabilities. The magnitude of the external field and the polarisabilities are systematically varied. The application of an external field (of sufficient magnitude) is found to induce chain formation (as expected). The monodisperse systems are found to ‘self-assemble’ with larger induced dipole moments effectively clustering in chains as a result of significant dipole-induced dipole effects. The distribution of the chain lengths is characterised as a function of the applied field and the atom polarisability. For the bidisperse systems, the external field induces chain formation and a partial segregation, in which the more polarisable species preferentially form chains. The chain lengths are again determined as a function of field strength and the atom polarisabilities. Scaling behaviour is analysed.     

On the Bethe–Wigner–Shapiro limit of the rate coefficient for the capture of a rotating quadrupolar polarisable diatom by an ion

The low-energy (Bethe–Wigner–Shapiro) behaviour of the rate coefficient for capture of a polarisable quadrupolar rotationally excited diatom by an ion is calculated. The multichannel character of capture shows itself in the dependence of the effective attractive potential on the intrinsic angular momentum of the diatom and in a nonadiabatic diagonal correction to the potential. The predicted energy dependence of the rate coefficients is compared with previous numerically accurate results for the capture of H₂ molecules by H₂⁺ ions.     

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

ABSTRACT

We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion–ion interactions are included at the centre of a Mie core; the ion–water interactions are also modelled with a Mie potential without an explicit treatment of ion–dipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion–ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion–solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment.     

Two-phonon Raman spectra of LiH and LiD crystals

The experimental two-phonon Raman spectra of LiD and LiH are reported here. A deformation dipole model formulated elsewhere for LiD is used to compute the lattice dynamics of LiD and LiH required in the Raman intensity calculations. The use of the same model for LiH is justified by the good agreement between the peak positions of the temperature-weighted two-phonon density of states and the various experimental spectra. The Raman intensity calculations are carried out by treating the second-order expansion coefficients in the polarisability tensor as adjustable parameters. The need for the parameters associated with the next-nearest-neighbor ions is clearly demonstrated for all the spectra. A single set of six parameters for the T₂₈ spectra and thirteen parameters for the E₈ (or A₁₈) spectra is found to explain all the experimental spectra of LiD and LiH quite well. Since the polarisability of Li⁺ is very small, the need for the second-neighbor positive-positive parameters reflects on the extended and highly polarisable nature of the H^? or D^? ion.     

Selective Quantification of Trace Silver in Water Samples by Displacement Solidified Floating Organic Drop Microextraction Coupled With Electrothermal Atomic Absorption Spectrometry

ABSTRACT

In this work, a novel displacement solidified floating organic drop microextraction (D-SFODME) technique was developed and coupled with electrothermal atomic absorption spectrometry (ETAAS) for the determination of trace silver in water samples without need of any masking agents. The method involved the formation of copper diethyldithiocarbamate (Cu–DDTC), extracted from the resultant Cu–DDTC with SFODME procedure using 1-undecanol. Then, the solidified floating organic drop was transferred into a sample solution containing silver ion, and another SFODME procedure was carried out. Trace Ag⁺ was selectively preconcentrated using 1-undecanol through a displacement reaction between Ag⁺ and the preconcentrated Cu-DDTC and the floating organic drop was diluted by ethanol for ETAAS detection. Interferences from coexisting heavy metal ions with lower stability of their DDTC complexes relative to Cu-DDTC were minimized. Under the optimal conditions, the limit of detection was 4.7 ng L^?1 (3σ) for silver with a sample volume of 5.0 mL, and an enrichment factor of 250 was achieved. The relative standard deviation under optimum conditions is 3.6% (n = 7). The proposed method was successfully applied to determine trace silver in some environmental samples with satisfactory results.     

Statistical theory of a solvated electron in an electrolyte

The behavior of a solvated electron in an electrolyte is investigated. The formalism of the theory is based on variational estimation of path integrals. It reduces the problem to the investigation of the self-consistent mean field produced by the ions and the electron. Mayer cluster expansions make it possible to take account of the short-range interactions and to find expressions for the effective potential of the electron and the electron-ion and electron-neutral atom correlation functions as a function of the macro-and microscopic parameters of electrolytes. In the limit of high ion densities the behavior of the electron is determined solely by the Coulomb interaction, which results in the formation of a polaron state. This state of the electron is virtually independent of the thermodynamic parameters of the electrolyte. In the opposite limit of low ion densities the electron forms a cavity state. The presence of ions results in additional localization of the electron and is manifested experimentally as a shift of the absorption band in the direction of high energies. The estimated shift for a hydrated electron agrees with the experimental data. Zh. éksp. Teor. Fiz. 115, 1463–1477 (April 1999)     

Evaluation of the spectroscopic constants of the modified rittner potential by the Simon-Parr-Finlan technique

A critical examination is shown of the modified Rittner potential by use of the Simon-Parr- Finlan (SPF) technique, including contributions from the polarisability of ions and the van der Waals term. We develop an equation for the SPF constants, which are related to spectroscopic constants and the polarisability of the constituent ions. Our analysis indicates excellent agreement for the dissociation energies of 20 alkali halides with available experimental data. We also cite theoretical values of the SPF coefficients Y₂₀ and Y₁₁ for the 20 alkali halides; these also compare favourably with experimental data.     

Relative energies of surface and defect states: ab initio calculations for the MgO (001) surface

We present the results of calculations of the energy levels of defects at the (001) surface of MgO relative to the top of the valence band and values of defect ionisation potentials and electron affinities. The calculations were made using an embedded cluster method in which a cluster of several tens of ions treated quantum mechanically is embedded in a finite array of polarisable and point ions modelling the crystalline potential and the classical polarisation of the host lattice. The calculated ionisation potential of the ideal surface, which fixes the position of the top of the valence band with respect to the vacuum level, is about 6.7 eV. This value is used as a reference for positioning the energy levels of three charge states of a surface anion vacancy, which are also calculated as ionisation energies with respect to the vacuum level. The surface and vacancy electron affinities are calculated using the same method. As a prototype low-coordinated surface site, we have considered a cube corner. Our calculations predict the splitting of the corner states from the top of the surface valence band by about 1.0 eV. Both unrelaxed and relaxed holes are strongly localised at the corner oxygen ion. The ionisation energies and electron affinities of the corner anion vacancy are calculated. The electrons in the F and F⁺ centres at the corner are shown to be significantly delocalised over surrounding Mg ions.     

Capacitance of anisotropic quantum dots

The many-electron ground states in anisotropic parabolic quantum dots are investigated, by means of an unrestricted Hartree–Fock method. From the total energy, both the chemical potential and the differential capacitance of quantum dots are calculated. The effect of the shell structure due to quantization appears clearly in the chemical potential and the capacitance. The difference of the calculated differential capacitance from the classical one is caused by both the exchange interaction and the quantization. As the vertical extent of a dot increases from two-dimensional limit, the change of capacitance is small owing to cancellation between changes of Hartree term and exchange term, except at special number of electrons.     

Effect of donor acceptor substitution position on the electrical responsive properties of azulene system: a computational study

Effect of donor–acceptor substitution position on the electrical responsive properties like polarisability, first hyper polarisability of donor–acceptor substituted azulene derivatives have been investigated using HF and Density functional theory with various hybrid functional and basis. It is observed that among the DFT methods, CAM-B3LYP hybrid functional with correlation consistent polarised triple-zeta, cc-pVTZ basis show less overestimated value of polarisability and first hyperpolarisability compare to other hybrid functional and it is again advantageous than HF with similar basis in term of its price and performance ratio. An apparent violation of minimum polarisability principle among the studied azulene derivatives are observed and it has been explain due to non-constancy of the potential functions upon substitution of donor (NMe₂) and acceptor (NO₂) groups at different position of azulene ring. Computed β_av values are in accordance with the extent of charge transfer character of the azulene with a few exceptions. Position of donor and acceptor group at the five- and seven-member ring also play a big role in determining the electrical responsive parameter has been discussed. It is also observed that 2 and 6 carbon atom of azulene are highly sensitive towards donor acceptor substitution.     

Potential use of small basis set on the calculations of electronic properties of some four-membered heterocycles: a conformational study

The potential use of small basis sets upon a low level of theory was studied on the calculations of electronic properties (dipole moment, static polarisability and static hyperpolarisabilities) of a series of 16 four-membered heterocycles with an exocyclic double bond at the position 3 (1–16). First, the calculations were performed within the Hartree–Fock (HF) approximation using 6-31G, 6-31G(d,p) and 6-31+G(d,p) as basis sets for the different conformational states of each molecule, and the results obtained were compared with the MP2/6-31+G(d,p) results reported. In the second place, in order to know the real potential of HF calculations, these were compared with those calculated using larger approaches such as MP2/6-311+G(d,p), MP2/aug-cc-pVDZ, CCS/6-311+G(d,p), CCS/aug-cc-pVDZ, CCS/aug-cc-pVTZ, CCSD/6-31+G(d) and CCSD/cc-pVDZ, taken into account only the planar and equilibrium geometries of each molecules. The HF approaches permit us to obtain a good qualitative representation of the dipole moment as a function of puckering angle in comparison with MP2, CCS and CCSD levels for all tested molecules. However, only HF/6-31+G(d,p) provides quantitative values of dipole moment for the heterocycles 1, 5 and 13 in comparison with MP2, CCS and CCSD levels. On the other hand, the polarisability and hyperpolarisabilities were quite sensitive to the quality of level of theory and basis sets. In particular, HF/6-31+G(d,p) predicted a representative approximation of alpha for the molecule 16 in comparison with larger methods as MP2/aug-cc-pVDZ, CCS/aug-cc-pVDZ and CCS/aug-cc-pVTZ, while a detailed analysis showed that HF can be used in the calculation of alpha for the molecules 3, 7, 11 and 15, but it requires the use of extended basis sets. Also, HF/6-31+G(d,p) predicted values of beta very similar to those calculated at the MP2 and CCSD levels used, for the planar and equilibrium geometry of the molecules 10 and 14. Furthermore, HF/6-31+G(d,p) described a representative dependence of this property with the puckering angle for the heterocycles 9, 10 and 14, compared with the MP2 curves.     

多铁材料BaCoF$lt;sub$gt;4$lt;/sub$gt;电子结构的第一性原理研究

采用基于密度泛函理论的广义梯度近似方法和赝势平面波法,对多铁材料BaCoF₄的铁电反铁磁相和可能的顺电相的电子结构进行了第一性原理研究.研究表明,反铁磁态很可能有利于低温下的铁电稳定性,F的强负电性使得体系内原子间主要是离子键相互作用.Co离子与在bc面上的F（2）,F（3）离子间完全是离子键作用,而与F（4）间有较弱的共价作用,与F（1）间作用介于两者之间.铁电畸变主要来源于Ba离子与F（1）, F（2）, F（3）离子沿着c轴方向的相对位移,F（4）对铁电性的贡献最少.铁电相中F（2）, F（3）离子的能量低于中心对称相,最大位移贡献者F（1）的化学键性由弱共价作用到离子键的变化也是最大的,这均有利于体系的稳定. 关键词： 第一性原理 铁电性 铁电畸变 反铁磁性     

Linear ion trap imperfection and the compensation of excess micromotion

Quantum computing requires ultracold ions in a ground vibrational state,which is achieved by sideband cooling.We report our recent efforts towards the Lamb-Dicke regime which is a prerequisite of sideband cooling.We first analyse the possible imperfection in our linear ion trap setup and then demonstrate how to suppress the imperfection by compensating the excess micromotion of the ions.The ions,after the micromotion compensation,are estimated to be very close to the Doppler-cooling limit.     

Off-centre charge model of the planar electric double layer for asymmetric 2:1/1:2 valencies

ABSTRACT

Grand canonical Monte Carlo simulation results are reported for the structure and capacitance of a planar electric double layer containing off-centre charged rigid sphere cations and centrally charged rigid sphere anions. The ion species are assigned asymmetric valencies, +2:?1 and +1:?2, respectively, and set in a continuum dielectric medium (solvent) characterised by a single relative permittivity. An off-centre charged ion is obtained by displacing the ionic charge from the centre of the sphere towards its surface, and the physical double layer model is completed by placing the ionic system next to a uniformly charged, non-penetrable, non-polarizable planar electrode. Structural results such as electrode-ion singlet distribution functions, ionic charge density and orientation profiles are complemented by differential capacitance results at electrolyte concentrations of 0.2?mol/dm³ and 1?mol/dm³, respectively, and for various displacements of the cationic charge centre. The effect of asymmetry due to off-centre cations and valency asymmetry on the double layer properties is maximum for divalent counterions and when the cation charge is closest to the hard sphere surface.     

Effect of oxidation state and coordination with Hg(II) on the electronic spectra of an anthraquinone–rhodamine sensor

ABSTRACT

In this study, a computational examination of the electronic transitions and through-space energy transfer processes lends insight into the experimental electronic spectra of a redox-sensitive rhodamine–anthraquinone dyad. Electronic transitions were calculated using density functional theory (DFT) and time-dependent DFT (TDDFT) based on models optimised from single-crystal X-ray diffraction (XRD) ion positions. DFT calculations were performed on gas-phase models using the Vienna Ab Initio Software Package (VASP) with the functional developed by Perdew, Burke, and Ernzerhof (PBE) on a basis set of plane waves. Using the DFT results, select transitions were evaluated based on a dipole–dipole coupling mechanism to find the Förster resonance energy transfer coupling, the square of which is approximately proportional to the rate of energy transfer between the donor and the acceptor. Electronic transitions during the relaxation of charge carriers are also investigated using nonadiabatic molecular dynamics. In order to investigate the transitions contributing to key peaks in the experimental absorbance spectra, TDDFT calculations were performed in Gaussian 09 with the B3LYP functional on the sensor in solution phase, which is simulated using a polarisable continuum model (PCM). The computed electron transfer process from the excited rhodamine to the quinone correlates better with the experimental data than does the computed Förster resonance energy transfer (FRET) process. This computed electron transfer process is faster than the radiative lifetime of the fluorescent state, which collectively suggests that the charge transfer process quenches fluorescence. These results support the observation that fluorescence is more prominent in the oxidised sensor than in the reduced sensor.     

Confinement effects on the spin potential of first row transition metal cations

Abstract

By using a spherical confinement method, the behaviour of spin potential and pairing energy is studied and compared to the free ion limit for a representative sample of first row transition metal cations. The study was carried out using three approximations within the Kohn–Sham model; exchange-only, exchange plus correlation contribution and correcting the self-interaction error. For the three approaches, the spin potential shows a close connection with the capability of a system to perform a spin-flip process. Namely, in accordance with Hund’s rule, the spin potential increases from low d occupation up to maximum for the half filled configurations; and it decreases from that point on, as d occupation grows. Such a conclusion is reached for confined and non-confined cations, even under extreme confinement conditions. In addition, two important observations are obtained: (a) In contrast to the neutral atoms situation, in the case of cations no eigenvalue crossings are observed under confinement conditions for the whole sample of ions tested. (b) The self-interaction error found in many exchange–correlation functionals does not affect the pairing energy over confined atoms, even when this error has an important contribution on a single eigenvalue. Therefore, pairing energy predicted by exchange–correlation functionals non-corrected by the self-interaction error can be made safely on transition metal cations under high pressures.     

Chemical bonding assisted damage production in single-walled carbon nanotubes induced by low-energy ions

Using first-principles molecular dynamics (MD) and classical MD simulations, we investigate the minimum energy required for various incident ions to displace a carbon atom in single-walled carbon nanotubes (CNTs), which is a key parameter to characterize the damage capability of the incident ion. The role of chemical aspects of incident ions played in the damage production mechanism was analyzed in details. The results indicate that the chemical bonding properties of impinging ions could greatly lower the threshold displacement energy of carbon atoms in CNTs, and thus considerably enhance their damage capabilities compared to those chemically inactive ions. The strong chemical interactions existing between ions and nanotubes can considerably increase the amount of damages, which is in contrast with the conventional conclusion that the damage yield increases monotonically with the atomic number of incident ion owing to its dependence on the cross section of defect production. This chemical bonding assisted damage process is clearly different from the damage process resulted only from physical collisions.     

Influence of size of solvent molecules on structural and thermodynamic properties of the electrode/electrolyte interface

The influence of size of solvent molecules on the structural and thermodynamic properties of the interface between the electrode and electrolyte, using the solvent primitive model, was studied by grand canonical Monte Carlo (GCMC) simulations. The computer simulation results are compared with those obtained from the modified Poisson–Boltzmann (MPB) theory. The ionic singlet distribution functions show that the solvent molecules of low diameter favour the counter ion adsorption on the electrode. With increasing diameter of the solvent molecules, the mean electrostatic potential increases, while the integral and differential capacitances decrease. The integral capacitance curves obtained by MPB theory are in qualitative agreement with those obtained by the GCMC simulation although the theoretical results are overestimated.     

Dynamic properties of aqueous electrolyte solutions from non-polarisable,polarisable, and scaled-charge models

We investigated the dynamic properties of alkali halide solutions (NaCl, NaF, NaBr, NaI, LiCl, and KCl) using molecular dynamics simulations and several non-polarisable, polarisable, and scaled-charge models. The concentration dependence of shear viscosity was obtained with low statistical uncertainties to allow for calculation of the viscosity Jones-Dole B-coefficients. No prior values are available for the B-coefficients from molecular simulations of fully atomistic models for electrolyte solutions. In addition, we obtained diffusion coefficients with rigorous finite-size corrections to access ion mobilities; these provide insights on single ion hydration behaviour. We find that all models studied, even polarisable and scaled-charge models, quantitatively over-predict water structuring but qualitatively follow the experimentally determined Hofmeister series. All ion models considered are kosmotropes based on their calculated B-coefficient and diffusion coefficients, even for ions experimentally found to be chaotropes. These observations indicate that the water-ion interactions in these models are not adequately represented; additional interactions such as charge transfer must be incorporated in future models in order to better represent electrolyte solution properties.