Photoelectron spectra and orbital assignments by sum rule consideration: Ethyl and n-propyl fluorides

The He I photoelectron (PE) spectra of C₂H₅F and n-C₃H₇F have been obtained. The PE spectra indicate that the first ionization potentials are about 0.4 eV higher than those of the parent alkanes owing to the inductive effect of fluorine. All the PE bands obtained here have been interpreted in terms of appropriate p-type localized MO's using the sum rule described previously by the authors. Orbital energy diagrams involving the inductive effect of fluorine are illustrated. The semi-empirical CNDO/2 and MINDO/2 methods were also employed to help confirm the present orbital assignments.     

UV photoelectron spectra and sum rule consideration: Out-of-plane orbitals of unsaturated compounds with planar-skeleton structure

He(l) photoelectron spectra are presented for various planar unsaturated aliphatic compounds such as mono- and di-methyl substituted ethylenes, alkyl aldehydes, chloro-substituted aldehydes, ketones and alkyl acids. Each photoelectron spectrum is resolved into individual bands by considering the band shape, the relative intensity and the number of p-type localized MO's (LO's). The sum rule previously proposed on vertical ionization energies by the present authors is applied to the photoelectron bands associated with out-of-plane LO's. In each compound, a partial sum P(a″) is obtained over all the out-of-plane LO's and it is shown that the calculated P(a″) value is in good agreement with the experimental one which may be obtained by an appropriate sum of vertical ionization energies with negative signs.     

Conformational effects on ionization potentials: Photoelectron spectra of dibromo- and bromofluoro-alkyl compounds

The photoelectron spectra of 6 dibromoalkanes and 9 bromofluoroalkanes have been recorded in the region of 10 to 11 eV, corresponding to the ionization of the n electrons of the bromine atom. For most of the compounds four peaks are observed. In the dibromoalkanes these correspond to a spin-orbit coupling of the two bromine atoms. In the bromofluoroalkanes the peaks have been assigned to two different conformations of the molecule, each giving rise to a doublet. This study shows that differences in the ionization potentials may exist between preferential conformations of a molecule.     

L-苯丙氨酸构象和电离能的理论研究

摘要: 我们对L-苯丙氨酸进行了全势能面搜索,采用B3LYP方法优化了L-苯丙氨酸的648种可能构象,最终得到了37种稳定存在的构象。分别采用B3LYP、B3PW91、M06-2X、MP2和CCSD(T)计算了L-苯丙氨酸最稳定的10种构象的相对能量,其中M06-2X和MP2方法能够给出较好的结果。对比不同的基组,说明采用aug-cc-pVDZ已经接近达到基组收敛极限。用电子传播子理论P3近似方法计算稳定构象外价壳层轨道的垂直电离能与光电子能谱实验符合的很好;根据构象的相对能量以及理论模拟与实验的光电能谱的比对,说明对气相光电子能谱至少四种构象有贡献.     

Photoelectron spectra of 1,2-indandione, 1,3-indandione and heterocyclic analogues

The photoelectron (He(I)) spectra of 1,2-indandione and heteroanalogues (coumarandione, thionaphthenequinone, and isatin), 1,3-indandione and heteroana     

Photoelectron spectra of carbonyls: Acetaldehyde,acetamide, biacetyl,pyruvic acid,methyl pyruvate and pyruvamide

Photoelectron spectra of a number of carbonyl compounds are reported and assigned on the basis of a correlative scheme which makes heavy use of CNDO/s computations. The assignments of n and π_○ type for monocarbonyls, and n₊, n_?, π_⊕ and π_? type for α-dicarbonyls are quite secure in an experimental sense. All other assignments given are tentative.     

Infrared spectra of the matrix-isolated chlorides of iron,cobalt, and nickel

Iron, cobalt, and nickel metal cathodes were sputtered with various mixtures of ³⁷Cl₂/³⁵Cl₂/Ar to produce Ar matrices at 14 K that contained the mono-, di-, and trichlorides of the corresponding metal. The measured infrared absorption spectra of these matrices allowed the identification and characterization of FeCl₂, FeCl₃, CoCl, CoCl₂, CoCl₃, and NiCl₂. The derived vibrational constants of the electronic ground state of ⁵⁹Co³⁵Cl are ω_e = 457.8 ± 3.0 cm^?1 and ω_eχ_e = 2.0 ± 1.5 cm^?1. The antisymmetric stretching mode frequencies of six isotopomers of FeCl₂ and three isotopomers of CoCl₂ were identified and measured. The dichlorides of iron, cobalt, and nickel were all determined, in contrast with previous work, to be nonlinear with bond angles of 161, 157, and 161°, respectively. The estimated uncertainty is 5°. For both iron and cobalt trichlorides, the measured stretching mode frequencies were used to derive a ClMCl angle in excess of 120°, as would be expected for planar molecules with somewhat anharmonic vibrations. Observed adsorption peaks could be assigned to the ν₃(E) modes of planar (D_3h) Fe and Co trichlorides and the corresponding modes of the isotopomers. These observations strongly suggest that recent data supporting a pyramidal geometry for FeCl₃ should be reexamined. The geometry of CoCl₃ has not previously been determined.     

Effect of chlorine substitution on triplet state structure of thioxanthone: A time‐resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time‐resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2‐chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of ³n–π* to ³π–π* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of multiple ionization on K-shell fluorescence yield transition energies and intensity ratios for argon

Theoretical calculations of ω_K, changes in the K_α and K_β X-ray energies and ratios of K_β and K_α intensities for multiply-ionized argon are presented using the nonrelativistic Hartree-Fock-Slater atomic model.     

Critical point energies from appearance potential spectra of cobalt,nickel, and copper

Structural features in soft X-ray appearance potential spectra (SXAPS) of cobalt, nickel, and copper previously assigned to collective excitations are shown to be due to corresponding structure in the s-p like density of states of these metals. By reference to theoretical work the critical points in the f.c.c. Brillouin zone responsible for these features are identified and experimental critical point energies are derived and compared to various band structure calculations.     

Photoelectron (He(I), He(II) and X-ray) spectroscopy of γ-pyrone and its related sulphur derivatives: valence and core ionization energies and shake-up satellites

The photoelectron He(I) and He(II) spectra of 4H-pyran-4-one (1), 4H-thiopyran-4-one (2), 4H-pyran-4-thione (3) and 4H-thiopyran-4-thione (4) are reported. The assignments are based on experimental evidence, taking into account the results of theoretical calculations. The outermost orbital sequences proposed (X = O, S) are n_X (σ), 3b₁ (π), 1a₂(π) for 1, 2 and 4; and 3b₁(π), n_X(σ) and 1a₂(π) for 3. The shifts of the core-ionization energy values for 1–4 are ascribed to a drift of π-charge from the intracyclic heteroatom towards the carbonyl or thiocarbonyl group. Low-energy shake-up satellites (up to 25% with respect to the main line) are observed in the various energy regions of the XPS spectra. They are qualitatively reproduced by CNDO/2 calculations. The most important satellites derive from the transition in the ion corresponding to the 3b₁ (π) → 4b₁(π*) transition in the UV-visible spectra of the neutral molecules. Charge rearrangements accompanying this transition lead to charge depletion of the core-ionized atom.     

Core binding energies for clusters deposited on different insulating substrates: esca spectra and theoretical electronic structure studies

The 4f core-level X-ray photoemission of small Pt clusters deposited on Teflon and SiO₂ substrates has been investigated. The experimental results are discussed and related to other data reported in the literature. Parallel results are presented for ab initio selfconsistent field, SCF, calculations of the core ionization potentials, IPs, of small Li clusters. These model calculations provide qualitative information about the nature and magnitude of the initial and final state contributions to the IPs for small clusters. We find that the binding energy shifts and linewidth broadening depend primarily on the cluster size and on the cluster substrate interaction. They do not result from electrostatic effects of the unit positive charge remaining on the ionized cluster. Our calculations show that this Coulomb effect does not apply to very small clusters.     

Quasiparticle energies,excitonic effects and optical absorption spectra of small-diameter single-walled carbon nanotubes

We present a first-principles study of the effects of many-electron interactions on the optical properties of single-walled carbon nanotubes. Motivated by recent experiments, we have carried out ab initio calculations on the single-walled carbon nanotubes (3, 3), (5, 0) and (8, 0). The calculations are based on a many-body Greens function approach in which both the quasiparticle (single-particle) excitation spectrum and the optical (electron–hole excitation) spectrum are determined. We show that the optical spectrum of both the semiconducting and metallic nanotubes studied exhibits important excitonic effects due to their quasi-one-dimensional nature. Binding energies for excitonic states range from zero for the metallic (5, 0) tube to nearly 1 eV for the semiconducting (8, 0) tube. Moreover, the metallic (3, 3) tube possesses exciton states bound by nearly 100 meV. Our calculated spectra explain quantitatively the observed features found in the measured spectra. PACS 78.67.Ch; 71.35.Cc; 73.22.-f     

Artificial peaks in energy dispersive X‐ray spectra: sum peaks,escape peaks,and diffraction peaks

Sum peaks, escape peaks, and diffraction peaks are considered artificial or spurious peaks in energy dispersive X‐ray spectrometry. Experimental examples are given, which showed that escape and diffraction peaks can add up to become sum peaks. These artificial peaks are not weak, and great care must be taken to differentiate them from peaks due to impurity or trace elements. The relationship between the intensity of a sum peak and the original peaks is illustrated using computer simulation as well as probability theory. Copyright © 2016 John Wiley & Sons, Ltd.     

Binding energies and K-edge spectra of NO chemisorbed on Ru(0001)

The electronic structures, adsorption energies and equilibrium geometries of chemisorbed NO on the Ru(0001) surface for several adsorption sites were determined using cluster models and employing the first principles, local density theory. Ground state one-electron eigenvalues and wave functions were obtained using the discrete variational method with numerical atomic bases. K-edge X-ray absorption spectra of both nitrogen and oxygen for each geometry were obtained using a scattered wave method. The effects of the surface on these spectra were studied by comparison with results from an isolated NO molecule and with the XPS and UPS experiments of Umbach et al. Both the NO and the NO-substrate vibration frequencies were calculated. Comparison between these theoretical results, recent electron energy loss spectra of Conrad et al. and early experiments of Thomas et al. suggests that NO is adsorbed only at threefold and top sites.     

The metal-surface selection rule for infrared spectra of molecules adsorbed on small metal particles

The metal-surface selection rule predicts that some infrared absorption bands should be absent from the spectra of molecules adsorbed on metal particles. It predicts that those bands corresponding to molecular vibrations with an oscillating dipole moment parallel to the surface should be suppressed. We calculate that this selection rule should apply to adsorption on metal particles larger than about 20 Å in diameter; for smaller particles the rule is weakened.     

A theoretical description of energy spectra and two-neutron separation energies for neutron-rich zirconium isotopes

Very recently the atomic masses of neutron-rich Zr isotopes, from ⁹⁶Zr to ¹⁰⁴Zr, have been measured with high precision. Using a schematic Interacting Boson Model (IBM) Hamiltonian, the evolution from spherical to deformed shapes along the chain of Zr isotopes, describing at the same time the excitation energies as well as the two-neutron separation energies, can be rather well reproduced. The interplay between phase transitions and configuration mixing of intruder excitations in this mass region is succinctly addressed.