Spectral-statistics properties of the experimental and theoretical light meson spectra

We present a robust analysis of the spectral fluctuations exhibited by the light meson spectrum. This analysis provides information about the degree of chaos in light mesons and may be useful to get some insight on the underlying interactions. Our analysis unveils that the statistical properties of the light meson spectrum are close, but not exactly equal, to those of chaotic systems. In addition, we have analyzed several theoretical spectra including the latest lattice QCD calculation. With a single exception, their statistical properties are close to those of a generic integrable system, and thus incompatible with the experimental spectrum.     

An experimental and computational study of the valence photoelectron spectra of halogenated pyrimidines

The electronic structures of pyrimidine and a selection of its halogen-substituted derivatives have been investigated using ultraviolet photoelectron spectroscopy and ab initio quantum chemical methods. Assignments are proposed for all of the features in the PES spectra by comparison with the vertical ionization energies of the molecular orbitals calculated using the partial third-order quasiparticle approximation as applied to electron propagator theory and a corrected density functional method based on the B3LYP functional. The shifts of the outermost five molecular orbitals of the pyrimidine ring structure in the halogen-substituted derivatives with respect to the binding energies of the equivalent orbitals in the parent pyrimidine molecule are discussed as a function of the identity and ring position of the halogen atom.     

Near-field optical microscope image formation: a theoretical and experimental study

A quantitative comparison between theory and experiment has been carried out for a collection-mode near-field optical microscope. A 30-nm (lateral dimension) cylindrical dielectric sample was imaged. This image was compared with the result of theoretical calculations that used a classical macroscopic nonglobal model based on the excitation theorem. Good agreement was obtained, with image inversion, edge enhancement, and edge asymmetry correctly predicted.     

The photoelectron spectra of N-bromo-methylamine and N,N-dibromo-methylamine

The UV photoelectron spectra of the reactive halamines, CH₃ NHBr (N-bromo-methylamine) and CH₃NBr₂ (N, N-dibromo-methylamine) have been obtained from measurements on the gas phase reaction products of CH₃NH₂ and Br₂. Spectrum-stripping was used to separate the two components from spectra obtained under different equilibrium conditions. The spectra correlate well with the results of molecular orbital calculations on the two molecules, and show that there is considerable pπ-pπ interaction in the NBr bond.     

Franck-Condon因子计算及甲醛光电子能谱的理论研究

本文凭借多振动模混合下任意维Franck-Condon重叠积分封闭表示,推导出三维三振动模FranckCondon重叠积分的解析表示式;基于厄米多项式的级数形式,得到计算三维三振动模Franck-Condon因子的一般代数表示式.另外,应用Franck-Condon因子的代数表示,研究甲醛光电子能谱的强度分布及振动结构.对于H2CO+(珟Β2A1)←H2CO(珘X1A1)离子化过程,基于ab initio力常数及几何参数,计算FranckCondon因子,得到光电子能谱的谱线相对强度.结果表明理论模拟得到的光电子能谱与实验上观测到的能谱达到较好的一致;基于光谱模拟使人们能够对实验谱给予合理解释以及对谱峰进行正确归属.     

Franck-Condon 因子计算及甲醛光电子能谱的理论研究

本文凭借多振动模混合下任意维Franck-Condon 重叠积分封闭表示,推导出三维三振动模Franck-Condon重叠积分的解析表示式;基于厄米多项式的级数形式,得到计算三维三振动模Franck-Condon 因子的一般代数表示式。 另外,应用Franck-Condon 因子的代数表示,研究甲醛光电子能谱的强度分布及振动结构。 对于H2CO+( 2A1)← H2CO( 1A1)离子化过程, 基于ab initio力常数及几何参数,计算Franck-Condon 因子,得到光电子能谱的谱线相对强度。 结果表明理论模拟得到的光电子能谱与实验上观测到的能谱达到较好的一致;基于光谱模拟使人们能够对实验谱给予合理解释以及对谱峰进行正确归属。     

Satellite structure in the photoelectron spectra of the core electrons of NO,N2O and H2O

Satellite structures have been observed in the photoelectron spectra of the core shells of nitric oxide, nitrous oxide and water. An attempt has been made to characterize the satellite structure in terms of monopole transitions resulting from electron shake-up. For this purpose comparisons of the observed excitation energies were made with optical data for both (1) the neutral molecules and (2) the analogous equivalent-core molecular ions. Using these energy comparisons and population densities for various molecular orbitals some assignments are made of the orbitals involved in electron shake-up as a function of the core vacancy.     

Finite-size effects in single chain magnets: an experimental and theoretical study

The problem of finite-size effects in s=1/2 Ising systems showing slow dynamics of the magnetization is investigated introducing diamagnetic impurities in a Co2+-radical chain. The static magnetic properties have been measured and analyzed considering the peculiarities induced by the ferrimagnetic character of the compound. The dynamic susceptibility shows that an Arrhenius law is observed with the same energy barrier for the pure and the doped compounds while the prefactor decreases, as theoretically predicted. Multiple spin reversal has also been investigated.     

Interpretation of the photoelectron spectra of OF2 and SF2

The photoelectron spectra of OF₂ and SF₂ are assigned, based on ab initio many-body Green's function calculations. In the energy range beyond about 20 eV the molecular orbital picture of ionization breaks down.     

A theoretical study of the photoelectron spectrum of atomic lithium

The 1s photoelectron spectrum of atomic lithium has been calculated for incident photon energies of 151 and 1487 eV. For this open-shell system there are four possible final-state manifolds for the residual ion, with symmetries ³S, ¹S, ³P^o and ¹P^o. The line energies for the first four members of each manifold have been calculated using relaxed Hartree—Fock or configuration interaction wavefunctions as required. The agreement with available optical data is excellent.The intensity expressions neglecting interchannel coupling have been evaluated to allow a comparison of line intensities between final-state manifolds and hence the synthesis of theoretical spectra. The variation of the spectral profile with photon energy is clearly demonstrated. Conjugate shake-up, as well as shake-up processes are predicted to be important at high photon energy.     

Cyanogen on Ni(110): an experimental and theoretical study

Adsorption of cyanogen, C₂N₂, on a Ni(110) surface has been investigated by combining low energy electron diffraction, thermal desorption and angular resolved ultra-violet photoemission experiments as well as model cluster calculations using the linear combination of Gaussian-type orbitals local density functional method as well as a force field approach. Results of mirror plane photoemission experiments on the ordered c(2 × 2) monolayer could be rationalized by invoking adsorbates bonded to the surface via the π electrons, with their axis oriented along the [001] direction, across the grooves of the (110) surface, leading to an assignment of all six adsorbate-derived valence orbitals. However, unlike in a previous study on the analogous chemisorption system Pd(110)/C₂N₂, only one mirror plane was detected. A possible tilt of the adsorbates in the (1 0) plane was related to crowding on the closer spaced nickel surface by estimating the lateral interaction within the adsorption layer using force field models. Electronic structure calculations on various chemisorption model clusters confirmed the experimental orbital assignment and the orientation of the adsorbate axis essentially along the [001] direction. Best agreement with UPS data was found for the orbital splitting pattern of an adsorption geometry where the C-N groups bind sideways on-top of nickel atoms in the first crystal plane. On the other hand, bonding along in the troughs of the (110) surface leads to a distinctly different ordering of the valence orbitals, at variance with the experimental assignment.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

An experimental and theoretical investigation of the valence shell photoelectron spectrum of cyanogen chloride

The valence shell photoelectron spectrum of cyanogen chloride has been studied using HeI and synchrotron radiation. In the outer valence region the molecular orbital model of ionization holds, and the main bands can be associated with single-hole states. However, in the inner valence region electron correlation effects become important, and these result in complex satellite structure being observed. Vertical ionization energies and spectral intensities have been computed using the Green's function approach, and the results have facilitated an interpretation of the experimental spectra. Photoelectron angular distributions and branching ratios have been measured and have been used to assess the bonding characteristics of the outer valence molecular orbitals. The experimental data for the 8σ orbital display an energy dependence which suggests that photoionization from this orbital may be influenced by the chlorine 3p Cooper minimum. The extent to which the 8σ orbital can be considered as a chlorine atom lone-pair is discussed. Vibrational structure has been observed in the [Xtilde] ²Π, Ã ²Σ⁺ and [Btilde] ²Π photoelectron bands recorded with HeI radiation, and has been assigned to progressions involving the ν⁺ ₁ and ν⁺ ₃ modes.     

Localization of light on a cone: theoretical evidence and experimental demonstration for an optical fiber

The classical rays propagating along a conical surface are bounded on the narrower side of the cone and unbounded on its wider side. In contrast, it is shown here that a dielectric cone with a small half-angle γ can perform as a high Q-factor optical microresonator which completely confines light. The theory of the discovered localized conical states is confirmed by the experimental demonstration, providing a unique approach for accurate local characterization of optical fibers (which usually have γ ~ 10(-5) or less) and a new paradigm in the field of high Q-factor resonators.     

Some anomalies in the Ne(I)(744/736 Å) photoelectron spectra of N2O

The Ne(I) 774/736 Å photoelectron spectra of N₂O are reported for the X?²Π state of N₂O⁺. The spectra in general do not show any autoionization behavior to the extent reported for CO₂ and CS₂. There is an apparent “enhancement” of the 101 level by the 744 Å line. In contrast to the He(I) 584 Å PES, the intensity ratio for the 100 and 001 levels are reversed when excited by Ne(I) 736 Å radiation.The spectra also show excitation to higher vibrational levels of N₂O⁺X²Π. This can be explained within the framework of autoionization of a Rydberg state whose core is similar to that of the B? state of N₂O⁺.     

A theoretical study of photoelectron spectra of NbO2, MoO2 and RuO2 by cluster models

DV-Xα calculations have been applied to various small clusters of rutile-family dioxides (NbO₂, MoO₂ RuO₂). It appears that by taking into consideration the potential due to the atomic charges, the density, the ionization cross sections of the energy levels, and by summing the density of states (DOS) of the two different clusters representing surface structures, computations on even small clusters provide information which compares well with the experimental XPS spectra.     

二维光栅与周期性缝隙阵列组合薄膜结构的杂散光抑制

传统方格型二维光栅与周期性缝隙阵列的组合薄膜结构具有雷达和光学波段双带通的电磁特性. 但由于其杂散光能量集中分布而严重制约它在高精度探测以及成像领域中的应用. 本文提出了一种全新的组合薄膜结构, 即由满足一定约束条件的圆孔型二维光栅和十字缝隙阵列构成. 基于Fraunhofer衍射理论建立组合薄膜结构标量衍射模型, 通过对比两种组合薄膜结构的衍射光分布, 理论分析与实验测试均表明: 圆孔型光栅与十字缝隙阵列组合薄膜结构不仅能够提高其光学透过率, 而且还使其杂散光分布均匀, 降低了其杂散光总比率, 从而有效抑制杂散光, 进一步增强了二维光栅与周期性缝隙阵列组合薄膜结构在实际光学系统中的可靠性. 关键词： 二维光栅 组合薄膜结构 衍射光强 杂散光     

Autler-Townes splitting in photoelectron spectra of K2 molecule

We investigate Autler-Townes splitting in the photoelectron spectra of K₂ molecule driven by pump-probe pulses via employing the time-dependent wave packet approach.It is found that the magnitude of Aulter-Townes splitting varies with the wavelength of the intense laser pulse.In particular,the phenomenon of Aulter-Townes splitting vanishes for the far-off resonance of the pump pulse.Also,the split peaks of Autler-Townes in the case of resonant pump pulse give us an approach to directly obtaining the transition dipole moment of a molecule.     

Electronic structure,chemical bonding and X-ray photoelectron spectra of light rare-earth oxides

The electronic structure of the light RE oxides CeO₂, Pr₂O₃ and Nd₂O₃ has been studied by the cluster discrete variational DV-X method and X-ray photoelectron spectroscopy. The interpretation of XPE spectra basing on the MO model is given. The various electronic states contributions to the chemical bonding in the oxides are investigated.