A comparative multi-property analysis of existing models for the He–N2 potential energy surface

The ability of an improved version of a recent three-dimensional ab initio potential energy surface for the He–N₂ interaction [Phys. Rev. A 66, 042703 (2002)], determined from high-level coupled-cluster calculations (including full singles and doubles, perturbative triples, and Brueckner orbitals), to predict scattering cross-sections and various bulk gas mixture properties is tested. The full three-dimensional potential energy surface has been employed for the calculation of vibrational relaxation rates, and a two-dimensional version (at a fixed N₂ bond length of 2.0743 a ₀) has been used for the calculation of molecular beam scattering cross-sections using quantum close-coupling methods and for the calculation of bulk gas phenomena using classical trajectory methods. The results obtained from the two-dimensional version of the present potential energy surface are compared with those obtained from three other recent accurate two-dimensional representations of the He–N₂ interaction.     

Electronic and optical properties of Sr3X2 (X=N,P, As,Sb and Bi) compounds: first principles study

ABSTRACT

Direct bandgap semiconductors are very essential to fulfil the demand for the advancement in optoelectronic devices. Therefore it is important to predict new potential candidates having such unique features. In current work, Sr₃X₂ (X=N, P, As, Sb and Bi) compounds have been reported for the first time by well trusted FP-APW+lo method. For the better prediction of the energy band gap, mBJ is used alongwith routine generalised gradient approximation (GGA). The results show small and direct energy band gaps at Γ-Γ symmetry points with magnitude in the range from 0.62?eV (Sr₃P₂) to zero energy band gap (Sr₃Bi₂). In partial density of state Sr-d state and X-p state are contributed in the band structure. The compounds show mostly covalent bonding nature. The frequecy dependent optical properties in the linear optical range are also investigated.     

Comparisons between statistics of low energy collision cascades generated by full molecular dynamics and by its binary collision approximation

Abstract

Collision cascades in Cu, Au and Cu₃Au are generated by full molecular dynamics (MD) and by its binary collision approximation (BCA) with the Marlowe program. Cu and Au primaries have 1 keV initial energy.

The same Molière repulsive potential is used in both models for close encounters. In the MD model, this potential is carefully splined to the pair component of the N-body potential developed by Ackland and Vitek. In the BCA, this N-body interaction is roughly modeled by a constant isotropic 4 eV binding energy of the target atoms to their rest positions.

Time distributions of the number of atoms moving with a total energy higher than a threshold value E _d are compared and discussed. Recoil range distributions during the cascade development are discussed as well. The agreement between MD and BCA is fairly good in all cases for E _d larger than about 3 eV. In the case of smaller E _d-values, the BCA may result in an overestimate of the number of moving atoms in the late development of the cascades. This discrepancy is suggested to originate in the lack of attractive forces between the moving particles and the surrounding atoms in the BCA.     

Transport properties of a binary mixture of CO2ben N2 from the pair potential energy functions based on a semi-empirical inversion method

The potential energy surface of a CO₂-N₂ mixture is determined by using an inversion method, together with a new collision integral correlation [J. Phys. Chem. Ref. Data 19 1179 (1990)]. With the new invert potential, the transport properties of CO₂-N₂ mixture are presented in a temperature range from 273.15 K to 3273.15 K at low density by employing the Chapman-Enskog scheme and the Wang Chang-Uhlenbeck-de Boer theory, consisting of a viscosity coefficient, a thermal conductivity coefficient, a binary diffusion coefficient, and a thermal diffusion factor. The accuracy of the predicted results is estimated to be 2% for viscosity, 5% for thermal conductivity, and 10% for binary diffusion coefficient.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

Charged cores in ionized He clusters

Experimental and theoretical studies in large ionic helium clusters have suggested the presence of a diatomic (and occasionally triatomic) charged molecular core surrounded by the other atoms which are bound to it by weaker interactions [1-3]. The understanding of the interactions between the system He ₂ ⁺ and an additional He atom of the cluster is therefore important in order to start modelling the full cluster interaction potential. In the present work we carry out a new set of calculations on the full potential and on the bound states supported by the He ₂ ⁺ isolated ion and further extend them to generate a Rigid Rotor (RR) potential energy surface (PES) for the triatomic system with He ₂ ⁺ kept at its equilibrium geometry (2.0 a.u.). The 13 bound states which were found and the overall angular anisotropy that exists for this Potential Energy Surface (PES) are discussed in detail. We additionally show results of calculations on the surface vibrational extension to nine different values of the He ₂ ⁺ interatomic distance, thereby generating a fuller, three-dimensional interaction potential. A simpler modelling of the latter via “Pseudo Rigid Rotor” calculations for the bound states with a vibrationally excited core is also presented and discussed.     

Theoretical studies of three-dimensional potential energy surfaces using neural networks and rotational spectra of the Ar–N2 complex

ABSTRACT

A new three-dimensional potential energy surface (PES) of the Ar–N₂ van der Waals complex is constructed using the neural network method based on ab initio data points at the CCSD(T) level. The aug-cc-pVQZ basis set is employed for all atoms with midbond functions. The vibrationally averaged PES V₀₀ is characterised by a global T-shaped minimum which occurs at R = 3.715 Å, θ = 90.0° with a well depth of 98.779 cm^?1. Based on our three-dimensional PES, bound-state calculations are performed for three isotopomers of Ar–¹⁴N₂, Ar–¹⁵N₂, and Ar–¹⁴N¹⁵N, and several intermolecular vibrational states are assigned by analysing the wavefunctions. Moreover, the averaged structural parameters are calculated and the pure rotational transition frequencies with J = 0--6 are predicted. The spectroscopic constants are determined by fitting the rotational energy levels. The theoretical results are in good agreement with experimental data and this work gives more accurate results than those determined previously for the Ar–N₂ complex.     

Theoretical study of stereodynamics for reaction O(3P)+HCl

<正>The vector correlation between products and reagents for reaction O(~3P)+HCl→OH+Cl is studied using a quasiclassical trajectory(QCT) method on the benchmark potential energy surface of the ground ~3A" state[Ramachandran and Peterson,J.Chem.Phys.119(2003)9550].The generalised differential cross section(2π/σ)(dσ_(00)/dω_t) is presented in the centre of mass frame.The distribution of dihedral angles,P(φr),and the distribution of angles between k and j', P(θ_r),are calculated.The influence of the collision energy and the influence of the reagent rotation and vibration on the product polarization are studied in the present work.The calculated results indicate that the rotational polarization of the product molecule is almost independent of collision energy but sensitive to the reagent rotation and vibration.     

Dirac Operators Coupled to the Quantized Radiation Field: Essential Self-adjointness à la Chernoff

We study the Dirac operator D ₀ in an external potential V, coupled to a quantized radiation field with energy H _f and vector potential A. Our result is a Chernoff-type theorem, i.e., we prove, for the operator D ₀+α · A+V +λ H _f with λ ∈{0, 1}, that the essential self-adjointness is not affected by the behavior of V at ∞.      

Isotopic effects of the N(2D) + H2 → NH + H reaction: a quantum time-dependent wave packet investigation

Based on the potential energy surface reported by Li and co-workers (J. Comput. Chem. 34 1686–1696 (2013)), the dynamics calculations of N(²D)?+?H₂(v ₀?=?0, j ₀?=?0) reaction and its isotopic variants HD and D₂ are studied using time-dependent wave packet method in the collision energy range of 0.01–1.0?eV. Dynamics properties such as reaction probability, differential cross section, and integral cross section are studied at state-to-state level of theory. Present values are compared with available theoretical and experimental results. The results indicate that the integral cross sections of N(²D)?+?D₂ reaction are in general good agreement with the experimental data at collision energy below 0.15?eV. The rotational state-resolved integral cross sections of N(²D)?+?H₂/HD/D₂ reactions are compared with experimental values for the first time, with the obtained values being in good agreement with the experimental data.     

Density functional study of ternary AuxAgyCuz and AuxAgyCuz+ clusters (x + y+z = 5, 6)

ABSTRACT

We report a theoretical investigation of neutral Au_xAg_yCu_z and cationic Au_xAg_yCu_z⁺ ternary clusters, for x?+?y+z?=?5 and 6. Our study is performed within density functional theory at the TPSSTPSS/SDD level. The geometries, chemical order, binding energy, mixing energy, second difference in the energy, adiabatic ionisation potential of these clusters are evaluated as a function of the whole concentration range. The most probable dissociation channels and the corresponding dissociation energies for the most stable clusters are also determined and discussed.     

Effect of the degree of ordering of structural vacancies on the fine structure of the valence-band top in cubic boron nitride

The electronic energy structure of the defect system of c-BN_x with ZnS-type structure is calculated in the multiple-scattering theory by the local coherent potential method. The cluster version of the MT approximation is used to calculate the crystal potential. The effect of the relaxation of the crystal lattice on the electronic structure of nonstoichiometric boron nitride c-BN_0.75 is studied and a comparison is made with the electronic energy structure of c-BN in the same approximation. Fiz. Tverd. Tela (St. Petersburg) 39, 1064–1065 (June 1997)     

Quasiclassical description of electronic supershells in simple metal clusters

A quasiclassical method for calculating shell effects, which has been used previously in atomic and plasma physics, is used to describe electronic supershells in metal clusters. An analytical expression is obtained, in the spherical jellium model, for the oscillating part of the binding energy of electrons of a cluster as a sum of contributions from supershells with quantum numbers 2n _r +l, 3n _r +l, 4n _r +l,... This expression is written in terms of the classical characteristics of the motion of an electron with the Fermi energy in a self-consistent potential. The conditions under which a new supershell appears and the relative contribution of this shell are investigated as a function of the cluster size and form of the potential. Specific calculations are performed for a “square well” of finite depth. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 5, 333–337 (10 September 1999)     

Dynamics of magnetic insulation failure and self-organization of an electron flow in a magnetron diode

The dynamics of back cathode bombardment (BCB) instability in a magnetron diode (a coaxial diode in a magnetic field, B ≡ B _0z ≡ B ₀) is numerically simulated. The quasi-stationary regime of electron leakage across the high magnetic field (B ₀/B _cr > 1.1, where B _cr is the insulation critical field) is realized. An electron beam in the electrode gap is split into a series of bunches in the azimuthal direction and generates the electric field component E _θ(r, θ, t), which accelerates some of the electrons. Having gained an extra energy, these electrons bombard the cathode, causing secondary electron emission. The rest of the electrons lose kinetic energy and move toward the anode. Instability is sustained if the primary emission from the cathode is low and the secondary emission coefficient k _se=I _se/I _{e, BCB} is greater than unity. The results of numerical simulation are shown to agree well with experimental data. A physical model of back-bombardment instability is suggested. Collective oscillations of charged flows take place in the gap with crossed electric and magnetic fields (E × B field) when the electrons and E × B field exchange momentum and energy. The self-generation and self-organization of flows are due to secondary electron emission from the cathode.     

Odd-even effect of the number of free valence electrons on the electronic structure properties of gold-thiolate clusters

ABSTRACT

It is essential to understand the intrinsic stability of the gold-thiolate clusters, which present extensive potential applications in many fields such as the catalysis, biomedicines and molecular machines. The electronic structures and aromaticity indexes of a series of Au_m(SH)_n (m, n?=?5–12) were comprehensively investigated through energetic, vibrational, magnetic, and electronic density properties, which are highly sensitive to the size and topological structure of the cluster. Generally, computational results of energy gap between the frontier molecular orbitals, normalized atomization energy (NAE), and electron localization function (ELF)-σ values exhibit the odd-even effect, in which clusters with the even number of free valence electrons, being reflected by the value of (m–n), possess relatively higher stability than the odd one. However, it is difficult to describe the stability of cluster with the sophisticated three-dimensional structure through one single aromaticity index such as the nucleus-independent chemical shift (NICS) value. Principal component analysis and clustering analysis of the calculation results of Au_m(SR)_n clusters suggest that the value of (m–n) and the Au₄ unit are important for predicting the stability of the Au clusters.     

Tunneling conductivity oscillations in a magnetic field in metal-insulator-narrow-gap-HgCdTe structures: The energy spectrum and spin-orbit splitting of 2D states

We study tunneling conductivity oscillations in a magnetic field in narrow-gap p-HgCdTe-oxide-metal (Yb, Al) structures. In tunnel structures with Yb we detect two types of tunneling conductivity oscillations. The first is related to the crossing of the Landau levels of two-dimensional (2D) states localized in the surface quantum well of the semiconductor, and has an energy E _F+eV, where E _F is the Fermi energy of the semiconductor and V is the bias voltage; the second has an energy E _F. We find that in such structures with an asymmetric quantum well there is strong spin-orbit splitting in the spectrum of the 2D states. In p-HgCdTe-oxide-Al tunnel structures the surface potential is much weaker and only oscillations of the first type are observed. We find that in such structures there is only one spin state of the 2D carriers, while the second is pushed into the continuous spectrum because of strong spin-orbit coupling. To analyze the experimental results we calculate the spectrum of 2D states localized in the surface quantum well in a semiconductor with a Kane dispersion law. We find that all the experimental results are in good agreement with the results of calculations. Finally, we discuss the features of “kinematically coupled” states in an asymmetric quantum well. Zh. éksp. Teor. Fiz. 112, 537–550 (August 1997)     

Theoretical study of stereodynamics for the O（3P） ＋ H2 → OH ＋ H reaction

This paper employs the quasi-classical trajectory calculations to study the influence of collision energy on the title reaction on the potential energy surface of the ground ³A' triplet state developed by Rogers et al. (J. Phys. Chem. A 2000 104 2308). It calculates the product angular distribution of P(θ_r), P(φ_r) and P(θ_r, φ_r) which reflects vector correlation. The distribution P(θ_r) shows that product rotational angular momentum vectors j' of the products are strongly aligned along the relative velocity direction k. The distribution of P(φ_r) implies a preference for left-handed product rotation in planes parallel to the scattering plane. Four different polarisation-dependent cross-sections are also presented in the centre-of-mass frame. Results indicate that OH is sensitively affected by collision energies of H₂.     

Molecular effect on interatomic potentials

Abstract

In the low energy atomic collision of ε ≤ 0.1, the energy dissipation of projectile ion is mainly by the nuclear stopping. In this energy range Z-oscillation appears on ranges and range stragglings. In order to explain this osciallation from the viewpoint of molecular effect on interatomic potentials, an extended Hückel method is adopted for potential calculation. The Z-dependence on interatomic potentials to describe respective atomic collisions is similar to that of Z ₁-range oscillation. It suggests a possibility of molecular effect on the Z ₁-range oscillation.     

Single-particle thermal diffusion of charged colloids: Double-layer theory in a temperature gradient

The double-layer contribution to the single-particle thermal diffusion coefficient of charged, spherical colloids with arbitrary double-layer thickness is calculated and compared to experiments. The calculation is based on an extension of the Debye-Hückel theory for the double-layer structure that includes a small temperature gradient. There are three forces that constitute the total thermophoretic force on a charged colloidal sphere due to the presence of its double layer: i) the force F _W that results from the temperature dependence of the internal electrostatic energy W of the double layer, ii) the electric force F _el with which the temperature-induced non-spherically symmetric double-layer potential acts on the surface charges of the colloidal sphere and iii) the solvent-friction force F _sol on the surface of the colloidal sphere due to the solvent flow that is induced in the double layer because of its asymmetry. The force F _W will be shown to reproduce predictions based on irreversible-thermodynamics considerations. The other two forces F _el and F _sol depend on the details of the temperature-gradient-induced asymmetry of the double-layer structure which cannot be included in an irreversible-thermodynamics treatment. Explicit expressions for the thermal diffusion coefficient are derived for arbitrary double-layer thickness, which complement the irreversible-thermodynamics result through the inclusion of the thermophoretic velocity resulting from the electric- and solvent-friction force.     

Theoretical study of the stereodynamics for the reaction F+HBr

The vector correlation between products and reagents for exothermic reaction F + HBr → HF + Br has been studied using a quasi-classical trajectory (QCT) method on the latest extended Lond–Eyring–Polanyi–Sato (LEPS) potential energy surface at three collision energies of 0.1 eV, 0.2 eV and 0.3 eV. Four polarization- dependent generalized differential cross-sections (2π/σ)(dσ₀₀/dω _t ), (2π/σ)(dσ₂₀/dω _t ), (2π/σ)(dσ₂₂₊/dω _t ), (2π/σ)(dσ_21?/dω _t ) have been presented in the centre of mass frame, respectively. The distribution of dihedral angle P(φ _r ), the distribution of angle between k and j ′ , P(θ _r ), are calculated. Both the influence of the collision energy and the influence of the reagent rotation on the product polarization have been studied in the present work, and the results indicate that the product rotational angular momentum j ′ is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The orientation of the HF product rotational angular momentum vector j ′ depends very sensitively on the reagent rotation and also effected by the collision energy.