Ionization Balance in Non-Local-Thermodynamic-Equilibrium Plasmas

A collisional-radiative model is developed for population calculations of plasmas in non-local thermodynamic equilibrium. The rate equations in detailed configuration accounting are solved to obtain ion populations. The configuration averaged rate coefficients are used in the rate equations. The cross sections are calculated based on the first perturbation theory. Wavefunctions required in cross section calculations are obtained by the Hartree-Fock-Slater self-consistent-field model. This kinetic model is applied to low- and medium-Z as well as high-Zplasmas. The results are compared with those of other theoretical models and experiments. The comparisons show that the present results of the mean charge statetheoretical ones, while for high-Z elements, the presentthe experimental ones.for low- and medium-Z elements agree well with other theoretical ones, while for high-Z elements, the present mean ionization stages are about two stages lower than the experimental ones.     

The atomic structure and the properties of ununbium (<Emphasis Type="Italic">Z</Emphasis> = 112) and Mercury (<Emphasis Type="Italic">Z</Emphasis> = 80)

A super heavy element Uub (Z = 112) has been studied theoretically in conjunction with rela-tivistic effects and the effects of electron correlations. The atomic structure and the oscillator strengths of low-lying levels have been calculated, and the ground states have also been determined for the singly and doubly charged ions. The influence of relativity and correlation effects to the atomic properties of such a super heavy element has been investigated in detail. The results have been compared with the properties of an element Hg. Two energy levels at wave numbers 64470 and 94392 are suggested to be of good candidates for experimental observations.     

Conformation effects on the molecular orbitals of serine

This paper calculates the five most stable conformers of serine with Hartree--Fock theory, density functional theory (B3LYP), Moller--Plesset perturbation theory (MP4(SDQ)) and electron propagation theory with the 6-311++G(2d,2p) basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Ser1 by rotation of C₂--C₃ (Ser4), C₁--C₂ (Ser5) and C₁--O₂ (Ser2 and Ser3). Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.     

Orientation Dependence of Photoelectron Angular Distribution in Nitrogen Molecule Irradiated by XUV Laser Field

We theoretically study the dependence of photoelectron angular distribution on laser polarization direction in nitrogen molecules.The approach is based on the time-dependent density functional theory at the level of local density approximation complemented by self-interaction correction.It is found that photoelectron emission in one photon regime could be considered as a probing tool for the main character of different types of molecular orbitals(a or π).The pattern of emitted photoelectrons strongly depends on the polarized angle of the laser,for a orbital,the number of photoelectron decreases with increasing the polarized angle,while for ir orbital,it has the inverse relation to the polarized angle,which reveals the multi-electron effect in molecules.On the other hand,concerning the total photoelectron emission,one should take into account a few occupied orbitals instead of only the outmost one.     

Experimental and Theoretical Investigation of Valence Orbitals in 1,4-Dioxane by Electron momentum Spectroscopy

The binding energy spectrum of all valence orbitals and the momentum distributions of highest occupied molecular orbital （HOMO： 8ag）, 7bu＋7ag, 4bu, 2bg ＋4ag and 2au in 1, 4-dioxane are investigated by electron momentum spectroscopy （EMS） with 600 eV impact energy. The experimental results are consistent with theoretical calcula- tions of C2h chair conformation using the Hartree-Fock method and density functional theory with 6-311＋＋G^＊＊ and AUG-CC-PVTZ basis sets.     

Construction of Different Kinds of Atomic and Molecular Orbitals Using Complete Orthonormal Sets of ψ^α-ETO in Single Exponent Approximation

Using complete orthonormal sets of ψ^α-exponential type orbitals in single exponent approximation the new approach has been suggested for construction of different kinds of functions which can be useful in the theory of linear combination of atomic orbitals. These functions can be chosen properly according to the nature of the problems under consideration. This is rather important because the choice of the basis set may be play a crucial role in applications to atomic and molecular problems. As an example of application, different atomic orbitals for the ground states of the neutral and the first ten cationic members of the isoelectronic series of He atom are constructed by the solution of Hartree-Fock-Roothaan equations using ψ^1, ψ^0 and ψ^-1 basis sets. The cMculated results are close to the numerical Hartree-Fock values. The total energy, expansion coefficients, orbital exponents and virial ratio for each atom are presented.     

Static dipole polarizabilities of Scn （n ≤15） clusters

The static dipole polarizabilities of scandium clusters with up to 15 atoms are determined by using the numerically finite field method in the framework of density functional theory. The electronic effects on the polarizabilities are investigated for the scandium clusters. We examine a large highest occupied molecular orbital --- the lowest occupied molecular orbital (HOMO--LUMO) gap of a scandium cluster usually corresponds to a large dipole moment. The static polarizability per atom decreases slowly and exhibits local minimum with increasing cluster size. The polarizability anisotropy and the ratio of mean static polarizability to the HOMO--LUMO gap can also reflect the cluster stability. The polarizability of the scandium cluster is partially related to the HOMO--LUMO gap and is also dependent on geometrical characteristics. A strong correlation between the polarizability and ionization energy is observed.     

Importance of Relativistic Effects for Intermediate-Z Elements： Photoionization Process of Excited Na

Using a modified R-matrix code, the fine-structure-resolved partial photoionization cross sections of excited Na （Z = 11） are calculated within the Breit-Pauli approximation. Our calculated energy levels of Na＋ and Na are in good agreement with the experimental values within 1% and the branching ratios of the J-resolved partial cross sections are consistent with the recent measurements within the experimental uncertainties. The agreements are impossible to be obtained without adequately taking into account the relativistic effects and the electron correlations together. Therefore, even for the intermediate-Z elements （e.g. Na with Z = 11）, the relativistic effects （mainly the spin-orbit interactions） should not be neglected.     

Large Eddy Simulation of Turbulent Channel Flow with 3D Roughness Using a Roughness Element Model

Large eddy simulation of turbulent channel flow with dense and small 3D roughness elements is carried out using a roughness element model Profiles of mean Reynolds stress, mean velocity and rms velocity as well as turbulent structures near the wall are obtained. The shear stress in the rough wall is larger than that in the smooth wall side and the rough wall has a larger influence on the channel flow. Profiles of mean streamwise velocity near the wall have logarithmic velocity distributions for both smooth and roughness walls, while there is a velocity decrease for the rough wall due to larger fractional drag. All the three components of rms velocities in the rough wall region are larger than that in the smooth wall region, and the roughness elements on the wall increase turbulent intensity in all directions. The s~reak spacing and average diameter of near wall quasi-s~reamwise vortices increase with the presence of roughness elements on the wall and it is shown that the rough wall induces complex and strong streamwise vortices. Results of dense and small 3D roughness elements in both turbulent statistics and structure, obtained with a relatively simple method, are found to be comparable to related experiments.     

Assessment of delocalized and localized molecular orbitals through electron momentum spectroscopy

Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.     

The theoretical and experimental investigations of Stark structure in sodium Rydberg states atoms

The experimental results of the Stark structure of Na in the vicinity of n~*=21-23 with the external electric field from 0 to 380V/cm are reported. The theoretical calculation of the stark levels of Na based on the atomic potential model are in good agreement with experiment. The limiting error between the theory and experiment turns out to be due to experimental uncertainty.     

An ergodic algorithm for long-term coverage of elliptical orbits

This paper deals with the coverage analysis problem of elliptical orbits. An algorithm based on ergodic theory, for long-term coverage of elliptical orbits, is proposed. The differential form of the invariant measure is constructed via the perturbation on mean orbital elements resulted from the J2 term of non-spherical shape of the earth. A rigorous proof for this is then given. Different from the case of circular orbits, here the flow and its space of the dynamical system are defined on a physical space, and the real-value function is defined as the characteristic function on station mask. Therefore, the long-term coverage is reduced to a double integral via Birkhoff-Khinchin theorem. The numerical implementation indicates that the ergodic algorithm developed is available for a wide range of eccentricities.     

Methyl orbital signatures in 2-amino-l-propanol

Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.     

Methyl orbital signatures in 2-amino-1-propanol

Electron density distributions of 2-aminoethanol (2AE) and 2-amino-1-propanol (2AP) are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.     

Stability of conductance oscillations in carbon atomic chains

The conductance stabilities of carbon atomic chains(CACs) with different lengths are investigated by performing theoretical calculations using the nonequilibrium Green's function method combined with density functional theory.Regular even–odd conductance oscillation is observed as a function of the wire length.This oscillation is influenced delicately by changes in the end carbon or sulfur atoms as well as variations in coupling strength between the chain and leads.The lowest unoccupied molecular orbital in odd-numbered chains is the main transmission channel,whereas the conductance remains relatively small for even-numbered chains and a significant drift in the highest occupied molecular orbital resonance toward higher energies is observed as the number of carbon atoms increases.The amplitude of the conductance oscillation is predicted to be relatively stable based on a thiol joint between the chain and leads.Results show that the current–voltage evolution of CACs can be affected by the chain length.The differential and second derivatives of the conductance are also provided.     

Systematic Calculation on Ground State Properties of Even-even Superheavy Nuclei Using Relativistic Mean Field Theory

In recent years the discovery of Super Heavy Element (SHE) with atomic number Z=108～116 has opened up a new era of research in nuclear physics, however, the extreme difficulties to synthesize SHE greatly restrict the experimental studies on it, so that the theoretical studies are very important. The Relativistic Mean Field theory (RMF) is proved to be a simple and successful theory due to its great success in describing the bulk properties at the β-stable valley, as well as nuclei far from the β-stable line, and gives good predictions for nuclei far beyond the end of the known periodic table. In the framework of RMF we have calculated the properties on SHN such as the binding energy, the deformation, single and double neutron separation energy, and the a-decay half-life and so on for nuclei Z=108～114 and N=156～190. The axial deformations considered by using the expansion of harmonic oscillator basis. The Lagrangian wc have used is as the following form:     

Electronic structure of PCBM

We have studied the electronic structure of [6,6]-phenyl-C₆₁-butyric-acid-methyl-ester (PCBM) using synchrotron radiation photoelectron spectroscopy (PES) measurements and first-principles calculations. The PES spectrum of the entire occupied valence band is reported, which exhibits abundant spectral features from the Fermi level to ～24 eV binding energy. All the spectral features are broadened as compared with the cases of C₆₀. The reasons for the broadening are analysed by comparing the experimental data with the calculated energy levels and density of states. Special attention is paid to the analysis of the C₆₀ highest occupied molecular orbital (HOMO)-1 derived states, which can play a crucial role in the bonding at the interfaces of PCBM/polymer blenders or PCBM/electrodes. Besides the well-known energy level splitting of the C₆₀ backbone caused by the lowered symmetry, C 2p states from the side chain mix or hybridize with the molecular orbitals of parent C₆₀. The contribution of the O 2p states can substantially modify the PES spectrum.     

Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies(BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory(DFT)(B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set(CBS-Q) method in conjunction with the 6311G** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.     

Electron Momentum Distributions of the Highest Occupied Molecular Orbital of CF3Br： Delocalization of Halogen Lone-Pair Orbitals

The highest occupied molecular orbital (HOMO) of trifluorobromomethane (CF3Br) is studied by binary (e,2e)electron momentum spectroscopy. The experimental momentum profile of the HOMO is compared with the Hartree-Fock (HF) and density functional theory (DFT-B3LYP) calculations. The calculated results largely depend on the size of basis sets rather than theoretical methods. Both the HF and DFT calculations using the 6-311 G^** basis set give a good explanation to the experiment. Delocalization of halogen lone-pair orbitals in the series molecules CF3X (X=F, Cl, Br) has been investigated.     

Simulating electron momentum spectra of iso-C2H2Cl2： A study of the core electronic structure

Electron momentum spectroscopy(EMS) has been used for the first time to study core electronic structure of isoC2H2Cl2. In the present work, the pronounced difference between ionization energies of two C1 score orbitals(2A1 and 3A1) is seen as a chemical shift of 3 eV, which is due to different chemical environments of the related carbon atoms. Both the calculated spherically averaged core electron momentum distributions(MDs) and three-dimensional electron momentum density maps show that these core molecular orbitals(MOs) 2A1and 3A1 exhibit strong atomic orbital characteristics in real and momentum space. However, the core states 2B2 and 4A1, which are almost degenerate and related to two equivalent atoms, exhibit notable differences between the momentum and position depictions. In contrast to the position space, the momentum density maps of these two core MOs highlight the interference effects which are due to the nuclear positions. The 2B2 orbital of iso-C2H2Cl2 is the antisymmetric counterpart of the 4A1 core orbital in real space. However, it relates to the 4A1 orbital by an exchange of maxima and minima in momentum space. Due to interference effects between electrons scattered from different atomic centers, modulations with a periodicity of 1.12 a.u. can be seen in the computed momentum densities, which tend to decay with increasing electron momenta. Accordingly, the EMS can not only effectively image the electronic structure of compounds by studying valence orbitals, but also provides direct information on the nature of the nuclear geometry by investigating the core states.