Photoelectron Spektra of Azabenzenes and Azanaphthalenes: II. A Reinvestigation of Azanaphthalenes by High-Resolution Photoelectron Spectroscopy

The bands with I_v < 13 eV in the photoelectron spectra of quinoline (IX), isoquinoline (X), cinnoline (XI), quinazoline (XII), and quinoxaline (XIII) have been reassigned in a way consistent with the assignment proposed for pyridine (II), the diazines (III, IV, V), s-triazine (VI), and 1,2,4,5-tetrazine (VII). The bands corresponding to the ejection of an electron from a π-orbital have been identified by a regression calculation based on a HMO perturbation treatment. It has been found that the combined through-space and through-bond interaction of the lone pairs in III, IV, V and in their corresponding benzologues XI, XII, XIII are the same within experimental error ( ±, 0.2 eV). Our assignment is also supported by an empirical correlation of the pK_{a, 1?} values and the mean lone-pair ionization potentials of the azaderivatives I to XIII.     

Photoelectron Spectra of Azabenzenes and Azanaphthalenes: III. The orbital sequence in methyl- and trimethylsilyl-substituted pyridines

The ionization potentials of methyl-, t-butyl- and trimethylsilyl-substituted pyridines have been determined by high-resolution photoelectron spectroscopy. The results are discussed in terms of destabilizing inductive and stabilizing conjugative effects of the substituents, and have been parametrized on the basis of a HMO-type perturbation treatment. Our data are in accord with the idea that the topmost occupied orbital in pyridine is a ‘lone pair’ orbital.     

Photoelectron Spectra of Unsaturated Oxides. I. 1,4-Dioxin and related systems

The He (Iα) photoelectron spectra of the four unsaturated oxides 3,4-dihydropyran ( 6 ), γ-pyran ( 7 ), 2, 3-dihydro-1, 4-dioxin ( 9 ) and 1, 4-dioxin ( 10 ) are reported and analysed. Band assignments are based on ab-initio calculations, using the STO-3G basis set. The proposed orbital sequences (with reference to the coordinate systems given in Table 1) are, for the top three orbitals: 6 , π, nσ, nπ; 7 , 3b₁(π), 1a₂(π), 11a₁(σ); 9 , 11b(π), 12a(σ), 11a(π); 10 , 2b_3u(π), 1b_1g(π), 6a_g(σ). Finally the (almost) localized π-orbitals have been computed by the Foster-Boys localization procedure.     

VUV photoionisation of free azabenzenes: Pyridine, pyrazine, pyrimidine, pyridazine and s-triazine

Photoionisation mass spectrometry was used to obtain the fragmentation pathways of pyridine, pyridazine, pyrimidine, pyrazine and s-triazine molecules upon absorption of 23.0, 15.7 and 13.8 eV synchrotron photons. The ionic fragments observed vary from molecule to molecule, however C₂H₂⁺, HCN⁺and HCNH⁺ are common to all five molecules at the three photon energies. Furthermore, the presence of C₂H₂N₂⁺, C₃H₃N⁺ and C₄H₄⁺ in the spectra of some of the molecules suggests dissociation pathways via loss of HCN moieties. The respective parent cations, m/q=79, 80 and 81 have a greater yield at low photon energies when compared to the most intense fragment peak in each spectra. We recorded two of the fragment cation yields, as well as the parent photoion yield curves of pyridine, pyridazine, and pyrimidine in the 8–30 eV range. The formation of abundant cation fragments show a strong propensity of the molecules for dissociation after the absorption of VUV photons higher than 14 eV. The differences in relative fragment yields from molecule to molecule, and when changing the excitation energy, suggest significant bond rearrangements and nuclear motion during the dissociation time. Thus, bond cleavage is dependent on the photon energy deposited in the molecule and on intramolecular reactivity. With the aid of photoion yield curves and energy estimations we have assigned major peaks in the spectra and discussed their fragmentation pathways.     

Photoelectron He(I) Spectra of small silanes

The photoelectron He(I) spectra of methyl-, dimethyl-, trimethyl- and ethylsiliane are reported and assigned with the help of CNDO/2 calculations.For each silane the ordering of the valence MO's obtained from calculations is, very close to that of the corresponding alkane, and is in agreement with spectral evidence. Participation of silicon d orbitals in bonding is not substantial but is more important in the outermost SiC and SiH MO's than in the π MO's mainly localized on the alkyl groups.     

ChemInform Abstract: Photoelectron Spectra of Cyclopolysilanes

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Photoelectron Spectra of Vicinal Tricarbonyls

The He I photoelectron spectra of tetramethylcyclopentane-1,2,3-trione 1 , 4,4,6,6-tetramethylcyclohexane-1,2,3-trione 2 , bicyclo[1.2.3]octane-2,3,4-trione 3 , bicyclo[2.2.3]nonane-2,3,4-trione 4 and anhydrous ninhydrine 5 are presented. The assignment of the first two bands is discussed using semiempirical calculations together with a qualitative band shape analysis. It is shown that the first two bands in 1 to 4 are due to the ionization of an electron from lone pair combinations of the 2p-oxygen orbitals.     

The Photoelectron Spectra of Ni,Pd, Pt-Diallyl

The He (I) photoelectron (PE.) spectra of bis (π-allyl)palladium (2a) , bis (π-allyl)platinum (3a) , bis (π-methallyl)palladium (2b) and bis (π-methallyl)-platinum (3b) have been recorded and compared with the PE. spectra of bis (π-allyl)nickel (1a) and bis (π-methallyl)nickel (1b) . By use of the He (II) PE. spectra 2a, 2b and 3b and correlations between the PE. spectra of 1–3 it is possible to assign the first seven to eight transitions in the PE. spectra of 1–3 . In contrast to previous assignments it is shown that the first band in the PE. spectrum of 1a corresponds to the ejection of an electron from 7a_u, a pure ligand orbital. The assignment proposed is supported by semiempirical calculations of the INDO-type by considering the relaxation effects explicitly using the ΔSCF and transition operator method.     

The Photoelectron Spectra of NSCl,NSF and NSF3

The photoelectron spectra of NSCl and NSF₃ have been recorded. By comparison with the PE.-bands of NSF and semiempirical calculations the first bands of NSCl and NSF₃ are assigned.     

Quadricyclanes. Part I: Photoelectron spectra and electronic structure

The photoelectron spectra of quadricyclane ( 3 ) and 3-methylidene quadricyclane ( 4 ) have been measured. The results served as a basis for the elucidation of the electronic structure of these compounds, which agreed with theoretical calculations. It is found that the symmetry of the HOMO of 3 is different when compared to that of its valence isomer norbornadiene ( 1 ). The results also indicate that the structure of the highest occupied orbitals cannot be derived by only considering the Walsh-orbitals of the two three-membered rings. In addition one of the Walsh-components of the four-memebered ring has to be taken into account.     

Analysis of azines and diazines by HPLC on bonded alkyl stationary phases. Pyridine and quinoline in environmental samples

Summary Several heterocyclic compounds have been investigated by HPLC on RP-8 and RP-18 with methanol-water mixtures as mobile phase. The chromatographic systems developed showed good selectivity for determination of azines and diazines. Pyridine and quinoline have been determined in environmental samples and in food. Samples for analysis were preconcentrated by solid phase extraction on-column with octadecyl silane packing.     

DFT Simulation of Electron Spectra for Auger Electron and Photoelectron Spectra of Lithium Compounds

(Li, O, F)-Auger electron, and X-ray photoelectron spectra (AES, VXPS) of solid lithium compounds (Li metal, LiCl, LiF, Li₂O) are simulated by deMon density functional theory (DFT) calculations using the model molecules of the unit cell. Calculated valence XPS, core-electron binding energies (CEBE)s, and Li-, O-, and F-KVV AES for the substances correspond considerably well to experimental results. For the calculation of VXPS, the observed spectra of Li₂O pellet with chemisorbed CO₂ almost show agreement with simulation curve of the valence XPS according to the model for the 1/1 ratio of Li₂O/Li₂CO₃. In the case of AES calculation, we analyze the experimental AES with our modified Auger electron kinetic energy calculation method which corresponds to the two final-state holes at the ground state and at the transition-state in DFT calculation by removing 1 and 2 electrons, respectively. Experimental KVV AES of the Li atom, and (O, F) KVV AES of (Li₂O and LiF) in the substances almost agree well to the AES calculated with maximum kinetic energies at the ground state, and at the transition-state, respectively.     

Photoelectron Spectra and Molecular Properties: Real-Time Gas Analysis in Flow Systems

For the analysis and optimization of numerous gas phase reactions in flow-systems, photoelectron spectroscopy has proven most valuable. This real-time measuring probe allows one to determine—with millimol quantities and within a few hours—the temperatures for different decomposition channels. Simultaneously, main products are characterized and, if need be, their yield can be improved. By careful performance of the experiment, short-lived and/or reactive molecules such as P₂, thioformaldehyde or silabenzene can be detected. PE-spectroscopic gas analysis is of particular advantage in the search for heterogeneous catalysts; they can be tested within a day using gas mixtures of varying composition over the temperature range from 300 K to 1300 K. In addition, PE-spectrometers are well-suited for on-line connection to computers; portable instruments for laboratory use are under development.     

Syntheses,Structures and Photoelectron Spectra of Phospha-Alkenes and Phospha-Alkynes and Their Transition Metal Complexes

Abstract

The chemistry of the novel phospha-alkenes RP[dbnd]CR'₂, and phospha-alkynes, RC[tbnd]P, containing 2pπ-3pπ bonds is of current interest.^1,2 Recent molecular orbital calculations,^3,4 suggest that the highest occupied molecular orbital in CH₂[dbnd]PH is of the π-type with the phosphorus lone pair ó-orbital only slightly more stable while the π? lumo orbital is relatively low lying. We now report He (I) photoelectron spectroscopic studies on a variety of RC[tbnd]P molecules^5,6 which indicate that the homo is also of the π-type and the π-σ separation is much greater than that found in the analogous RC[tbnd]N systems.     

Photoelectron Spectra of Nonmetal Compounds and Their Interpretation by MO Models

The results of (low energy) photoelectron spectroscopy render possible a better appreciation of the “Nature of the Chemical Bond”. The application of this new experimental method is demonstrated utilizing representative compounds of the nonmetal elements, and a close symbiosis delineated with molecular orbital models. In particular, general consequences are discussed concerning electron deficiency, σ- and π-interactions, electron pair delocalization, and substituent effects or geometric perturbations. Photoelectron spectroscopic ionization energies permit evaluation of parameters for specified molecular groups, allow correlation with numerous other experimental data, and are didactically valuable in the teaching of general chemistry.     

PAN和PPN的HeI光电子能谱（PES）

给出了两个重要的大气污染化合物PAN和PPN的紫外光电子能谱（PES）。为了 指认PES谱,对两个分子实施了HF和OVGF方法的理论计算,并给出了它们各自的优 化几何构型、PES谱低电离能区的两个分离（PAN）为11.42 eV和12.07 eV;PPN为 11.08 eV和11.79 eV）被归于分子中主要体现“NO_2”基团贡献的最高占有分子轨 道（HOMO）和次最高占有分子轨道（SHOMO）电子电离作用结果。而PPN的第一电离 能11.08 eV低于PAN的11.42 eV,是由于PPN分子中增加的“CH_2”基团电子的给予 作用,这为PPN应具有较大的生物毒性提供合理的解释。