Theoretical prediction on HBeN− and HNBe− anions using multiconfiguration second‐order perturbation theory

The HBeN^? and HNBe^? anions have been investigated for the first time using the CASSCF, CASPT2, and DFT/B3LYP methods with the contracted atomic natural orbital (ANO) and cc‐pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO and B3LYP/cc‐pVTZ levels. The ground and the first excited states of HBeN^? are predicted to be X²Π and A²Σ⁺ states, respectively. It was predicted that the ground state of HNBe^? is X²Σ⁺ state. The A²Π state of HNBe^? has unique imaginary frequency. A bend local minimum M1 was found along the 1²A″ potential energy surface and the A²Π state of HNBe^? should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves of isomerization reactions were calculated as a function of HBeN bond angle. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Evaluation of Orbital- and Ground State Energies of Some Open- and Closed-Shell Atoms over Integer and Noninteger Slater Type Orbitals

Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.     

From Electronegativity towards Reactivity—Searching for a Measure of Atomic Reactivity

Pauling introduced the concept of electronegativity of an atom which has played an important role in understanding the polarity and ionic character of bonds between atoms. We set out to define a related concept of atomic reactivity in such a way that it can be quantified and used to predict the stability of covalent bonds in molecules. Guided by the early definition of electronegativity by Mulliken in terms of first ionization energies and Pauling in terms of bond energies, we propose corresponding definitions of atomic reactivity. The main goal of clearly distinguishing the inert gas atoms as nonreactive is fulfilled by three different proposed measures of atomic reactivity. The measure likely to be found most useful is based on the bond energies in atomic hydrides, which are related to atomic reactivities by a geometric average. The origin of the atomic reactivity is found in the symmetry of the atomic environment and related conservation laws which are also the origin of the shell structure of atoms and the periodic table. The reactive atoms are characterized by degenerate or nearly degenerate (several states of the same or nearly the same energy) ground states, while the inert atoms have nondegenerate ground states and no near-degeneracies. We show how to extend the use of the Aufbau model of atomic structure to qualitatively describe atomic reactivity in terms of ground state degeneracy. The symmetry and related conservation laws of atomic electron structures produce a strain (energy increase) in the structure, which we estimate by use of the Thomas-Fermi form of DFT implemented approximately with and without the symmetry and conservation constraints. This simplified and approximate analysis indicates that the total strain energy of an atom correlates strongly with the corresponding atomic reactivity measures but antibonding mechanisms prevent full conversion of strain relaxation to bonding.     

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4]+

The tetraoxido ruthenium(VIII) radical cation, [RuO₄]⁺, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO₄]⁺, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO₄]⁺ is identified by the chemical shift at the ruthenium M₃ edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO₄]⁺ to the closed-shell [RuO₄H]⁺ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO₄]⁺ than for [OsO₄]⁺.     

Semiclassical analysis for highly degenerate potentials

This paper characterizes the semi-classical limit of the fundamental energy,

and ground state of the Schrödinger operator in a bounded domain , in the highly degenerate case when and consists of two components, say and . The main result establishes that

and that approximates in the ground state of in if

     

Unscented Kalman filter for time varying spectral analysis of earthquake ground motions

A novel parametric time-domain method for time varying spectral analysis of earthquake ground motions is presented. Based upon time varying autoregressive moving average (ARMA) modeling of earthquake ground motion, unscented Kalman filter (UKF) is used to estimate the time varying ARMA coefficients. Then, time varying spectrum is yielded according to the time varying ARMA coefficients. Analysis of the ground motion record El Centro (1940, N–S) shows that compared to Kalman filter (KF) based method, short-time Fourier transform (STFT) and wavelet transform (WT), UKF based method can more reasonably represent the distribution of the seismic energy in time–frequency plane, which ensures its better ability to track the local properties of earthquake ground motions and to identify the systems with nonlinearity. Analysis of the seismic response of a building during the 1994 Northridge earthquake shows that UKF based method can be potentially a useful tool for structural damage detection and health monitoring. Lastly, it is found that the theoretical frequency resolving power of ARMA models usually neglected in some studies has considerable effect on time varying spectrum and it is one of the key factors for ARMA modeling of earthquake ground motion.     

Multiplicity of solutions for Kirchhoff type equations involving critical Sobolev exponents in high dimension

In this paper, we study the following Kirchhoff‐type elliptic problem where is a bounded domain with smooth boundary ?Ω, a,b,λ,μ > 0 and 1 < q < 2^?=2N/(N ? 2). When N = 4, we obtain that there is a ground state solution to the problem for q∈(2,4) by using a variational methods constrained on the Nehari manifold and also show the problem possesses infinitely many negative energy solutions for q∈(1,2) by applying usual Krasnoselskii genus theory. In addition, we admit that there is a positive solution to the equations for N≥5 under some suitable conditions. Copyright © 2016 John Wiley & Sons, Ltd.     

Ground state solutions and geometrically distinct solutions for generalized quasilinear Schrödinger equation

In this paper, we study the following generalized quasilinear Schrödinger equation where N≥3, is a C¹ even function, g(0) = 1 and g^′(s) > 0 for all s > 0. Under some suitable conditions, we prove that the equation has a ground state solution and infinitely many pairs ±u of geometrically distinct solutions. Copyright © 2016 John Wiley & Sons, Ltd.     

Positive ground state of coupled systems of Schrödinger equations in involving critical exponential growth

In this paper, we study the existence of a positive ground state solution to the following coupled system of nonlinear Schrödinger equations: where the nonlinearities f₁(x,s) and f₂(x,s) are superlinear at infinity and have exponential critical growth of the Trudinger‐Moser type. The potentials V₁(x) and V₂(x) are nonnegative and satisfy a condition involving the coupling term λ(x), namely, λ(x)²<δ²V₁(x)V₂(x) for some 0<δ<1. For this purpose, we use the minimization technique over the Nehari manifold and strong maximum principle to get a positive ground state solution. Moreover, by using a bootstrap argument and L^q‐estimates, we get regularity and asymptotic behavior.