Investigation of outer valence orbital of CF2Cl2 by a new type of electron momentum spectrometer

Electronic states of CF2Cl2 （dichlorodifluoromethane, Freon 12） have been studied using a new type of electron momentum spectrometer with a very high efficiency at an impact energy of 1200 eV plus binding energy. The experimental electron momentum profiles are compared with the density functional theory （DFT） and Hartree-Fock （HF） calculations. The relationship between orbital assignments in different coordinate systems is discussed. A new method of difference analysis based on the new type of electron momentum spectrometer is used to clarify the ambiguities regarding the orbital ordering.     

Experimental and calculated momentum densities for the complete valence orbitals of the antimicrobial agent diacetyl

The first electronic structural study of the complete valence shell binding energy spectra of the antimicrobial agent diacetyl, encompassing both the outer and inner valence regions, is reported. The binding energy spectra as well as the individual orbital momentum profiles have been measured by using a high resolution （e, 2e） electron momentum spectrometer （EMS） at an impact energy of 1200eV plus the binding energy, and using symmetric noncoplanar kinematics. The experimental orbital electron momentum profiles are compared with self-consistent field （SCF） theoretical profiles calculated using the Hartree-Fock approximation and Density Functional theory predictions in the target Kohn-Sham approximation which includes some treatment of correlation via the exchange and correlation potentials with a range of basis sets. The pole strengths of the main ionization peaks from the inner valence orbitals are estimated.     

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.     

Distorted Wave Effects of the 1b3g Orbital in Ethylene

We study the unexpected distorted wave effects of the 1b3g orbital in ethylene using a high resolution binary (e,2e) electron momentum spectrometer,at an impact energy of 800eV plus the binding energy (8-22eV) with symmetric non-coplanar kinematics.The experimental monentum profile of the 1b3g orbital is obtained and compared with the data previously measured at an impact energy of 1200 eV plus the binding energy.Also,the experimental momentum profiles of the 1b3g orbital are compared with the theoretical momentum distributions calculated by using Hartree-Fock and density functional theory methods.The experimental momentum profiles of the 1b3g orbital of ethylene at different impact energies show that the cross section of the orbital below the momentum p-1 a.u.is higher for lower impact energies.     

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.     

Electron momentum spectroscopy of NF3

The electronic structure of nitrogen trifluoride was investigated by combining the high-resolution electron momentum spectroscopy with the high-level calculations. The experimental binding energy spectra and the momentum distributions of each orbital were compared with the results of Hartree-Fock, density functional theory （DFT）, and symmetry-adapted- cluster configuration-interaction （SAC-CI） methods. SAC-CI and DFT-B3LYP with the aug-cc-pVTZ basis set can well reproduce the binding energy spectra and the observed momentum distributions of the valence orbitals except 1 a2 and 4e orbitals. It was found that the calculated momentum distributions using DFT-B3LYP are even better than those using the high-level SAC-CI method.     

KLn Dielectronic Recombination Process of B- Through He-like Cu Ions

The KLn dielectronic recombination processes of trapped highly charged B-like through He-like Cu ions are studied theoretically, and the theoretical results are used to analyse our previous experimental data at Heidelberg electron beam ion trap （EBIT）. The theoretical resonant positions agree with the experimental resonant positions to a precision of 0.4%, in comparison with the resonant positions of those highest peaks between theory and experiment. The experimental spectra are then fitted using a formula with the theoretical resonant energies and strengths, the result shows good overall agreement between theory and experiment over a wide electron energy range. The distribution of highly charged states is obtained from the fitting parameters.     

Electron Momentum Spectroscopy of the Frontier Orbitals of Chlorodifluoromethane

We report on the first measurement of the electron momentum distributions of the three outermost valence orbitals for chorodifluoromethane(CHF2Cl)by binary(e,2e) electron momentum spectroscopy.The experimental data are compared with Hartree-Fock and density functional theory(DFT) calculations employing 6-31G,6-311 G^** and AUG-cc-pVQZ basis sets.For the summed momentum distribution of 8α′ 5α″ 7α′ orbitals,the DFT/.AUG-cc-pVQZ calculation gives the best fit.A very large and diffuse basis set,AUG-cc-pVQZ,is employed in the calculations to approach the Hartree-Fock limit of the basis set,but the improvement of the calculation quality is little in comparison with that calculated with the 6-311 G^** basis set,This indicates that the 6-311 G^** basis set is nearly saturated for the calculations of these three orbitals of CHF2Cl,and it is unnecessary to employ a larger basis set in the calculations.     

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.     

Post-collision interactions and the polarization effect in （e, 2e） collisions of helium

A modified distorted-wave Born approximation (DWBA) method is used to calculate the triple differential cross sections (TDCSs) in a coplanar asymmetric geometry for the electron impact single ionization of a He (1s2) atom at intermediate and lower energies. The post-collision interaction and the polarization effect in (e, 2e) collisions of helium are considered in the calculations. The polarization potentials from the damping method and density functional theory (DFT) are compared. Theoretical results are compared with the recent experimental data.     

Properties of A = 7-9 Drip-Line Nuclei in RMF Theory

The relativistic mean-field （RMF） theory is used to calculate the properties of A =7-9 drip-line nuclei ^7Li, ^7;9Be, ^8;9B, and ^9C. Systematic deviations between experimental and theoretical binding energies are found. Possible reasons of these systematic deviations are discussed in terms of pairing energy. The root-mean-square （rms） radii of matter distributions for these nuclei agree with the experimental data quite well. The one-proton halo structure in ^8B is reproduced well, and the two-proton halo in ^9C is predicted. The calculations show that the RMF theory is valid in studying the properties of light drip-line nuclei.     

Theoretical analysis on fully differential cross sections for C~(6+)impact ionization of helium

Fully differential cross sections （FDCS） are calculated within a four-body model for single ionization of helium by C6＋ impact at the incident energy of 100 MeV/a.u. （atomic unit）. The results are compared with experimental data and other theoretical predictions. It is shown that our results are in very good agreement with experiment for three small momentum transfers in the scattering plane; however, some significant discrepancies are still present at the largest momentum transfer in both the scattering plane and the perpendicular plane. In actuality, the problem has not been explained by the theory during the last decade. Accordingly, the contributions of different scattering amplitudes to FDCS are analyzed. It is found that for the largest momentum transfer the cross section arising from a destructive interference of the three amplitudes is much smaller than the experimental data. However, the cross section due to the constructive interference of two scattering amplitudes between projectile-ionized electron interaction and projectile-passive electron interaction almost approaches the experimental data.     

Investigations of the dielectronic recombination of phosphorus-like tin at CSRm

The electron–ion recombination for phosphorus-like~(112) Sn~(35+)has been measured at the main cooler storage ring of the Heavy Ion Research Facility in Lanzhou, China, employing an electron–ion merged-beams technique. The absolute total recombination rate coefficients for electron–ion collision energies from 0 e V–14 e V are presented. Theoretical calculations of recombination rate coefficients were performed using the Flexible Atomic Code to compare with the experimental results. The contributions of dielectronic recombination and trielectronic recombination on the experimental rate coefficients have been identified with the help of the theoretical calculation. The present results show that the trielectronic recombination has a substantial contribution to the measured electron–ion recombination spectrum of~(112)Sn~(35+). Although a reasonable agreement is found between the experimental and theoretical results the precise calculation of the electron–ion recombination rate coefficients for M-shell ions is still challengeable for the current theory.     

Extended Holstein polaron model for charge transfer in dry DNA

The variational method is applied to the study of charge transfer in dry DNA by using an extended Holstein small polaron model in two cases: the site-dependent finite-chain discrete case and the site-independent continuous one. The treatments in the two cases are proven to be consistent in theory and calculation. Discrete and continuous treatments of Holstein model both can yield a nonlinear equation to describe the charge migration in an actual long-range DNA chain. Our theoretical results of binding energy E_b, probability amplitude of charge carrier \phi and the relation between energy and charge--lattice coupling strength are in accordance with the available experimental results and recent theoretical calculations.     

Structure and analytical potential energy function for the ground state of the BCx (x=0, －1)

In this paper, the electronic states of the ground states and dissociation limits of BC and BC- are correctly determined based on group theory and atomic and molecular reaction statics. The equilibrium geometries, harmonic frequencies and dissociation energies of the ground state of BC and BC- are calculated by using density function theory and quadratic CI method including single and double substitutions. The analytical potential energy functions of these states have been fitted with Murrell-Sorbie potential energy function from our ab initio calculation results. The spectroscopic data （αe, ωe and ωeχe） of each state is calculated via the relation between analytical potential energy function and spectroscopic data. All the calculations are in good agreement with the experimental data.     

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.     

Optical Properties of Hexagonal and Cubic ZnS Nanoribbons: Experiment and Theory

Optical properties of hexagonal and cubic ZnS nanoribbons are studied by using valence electron energy loss spectroscopy （VEELS） and ab initio band structure calculations. The peaks in VEELS are assigned to interband transitions by comparing the interband transition strengths with the calculated densities of states. The optical properties are deduced from the experimental VEELS, and the theoretical calculations give consistent results. This combination of experimental and theoretical approaches provides a comprehensive understanding of the optical properties of polytype ZnS.     

Ground-State Properties ,of C, O, and Ne Isotopes in Hartree——Fock-Bogoliubov Calculation with Gogny Interaction

Ground-state properties of C, O, and Ne isotopes are described in the framework of Hartree-Fock-Bogoliubov theory with density-dependent finite-range Gogny interaction D1S. We include all the contributions to the Hartree-Fock and pairing feld arising from Gogny and Coulomb interaction as well as the center of mass correction in the numerical calcu/ations. These ground-state properties of C, O, and Ne isotopes are compared with available experimental results, Hartree-Fock plus BCS, shell model and relativistic Hartree--Bogoliubov calculations. The agreement between experiments and our theoretical results is pretty well. The predicted drip-line is dependent strongly on the model and effective interaction due to their sensitivity to various theoretical details. The calculations predict no evidence for halo structure predicted for C,O, and Ne isotopes in a previous RHB study.     

Polarization effect in （e, 2e） reaction process for Ar （3s） in coplanar asymmetric geometry

The （e, 2e） triple differential cross sections （TDCSs） of Ar （3s） are calculated by using distorted-wave Born approx- imation under coplanar asymmetric geometry. The incident electron energy is 113.5 eV, and the scattering electron angle 01 is -15~. The ejected electron energy is set at 10 eV, 7.5 eV, 5 eV, and 2 eV, respectively. The polarization effects have been discussed and the polarization potential Vpol changing from a second-order to a fourth-order term has been analyzed. Our calculated TDCSs have been compared with reported experimental and theoretical results, and the calculated TDCSs of polarization potential up to the fourth order could give a good fit with experimental results in the binary region, but fail to predict the correct recoil-to-binary ratio in most cases.     

Theoretical calculation of of B-like ions： photoionization cross sections N^2＋, O^3＋ and F^4＋

There can be found some notable discrepancies with regard to the resonance structures when R-matrix calculations from the Opacity Project and other sources are compared with recent absolute experimental measurements of Bizau et al [Astron.Astrophts.439 387(2005)] for B-like ions N2+,O3+ and F4+.We performed close-coupling calculations based on the R-matrix formalism for the photoionizations of ions mentioned above both for the ground states and first excited states in the near threshold regions.The present results are compared with experimental ones given by Bizau et al and earlier theoretical ones.Excellent agreement is obtained between our theoretical results and the experimental photoionization cross sections.The present calculations show a significant improvement over the previous theoretical results.