Carbon K-shell excitation spectra of linear and branched alkanes

The electron energy loss spectra of ethane, propane, n-butane, n-pentane, n-hexane, isobutane, isopentane and neopentane in the region of carbon K-shell excitation have been recorded under dipole-dominated conditions (2.8 ke V impact energy, small angle). The spectra are dominated by transitions to unoccupied valence π¹(CH₂, CH₃) and σ¹(C-C) levels. Additional weak features are assigned to Rydberg transitions. The position of the main continuum feature in each spectrum is consistent with the predictions of an empirical relationship with bond length. Systematic variations of spectral intensities are observed which support our assignments. The dominant feature in the K-shell spectrum of ethane, which was previously assigned to C 1s → 3p Rydberg transitions, is reassigned to excitation to a 3p/π¹(CH₃ ), mixed Rydberg/valence orbital (of antibonding σ-¹(C-H) character), in comparison to the other alkane spectra. An improved calibration value of 290.74(5) eV for the energy of the C 1s → π¹ transition in CO₂ is also obtained.     

Electron impact spectra of some alkyl derivatives of water and related compounds

Electron impact energy loss spectra at impact energies of 100 eV and 50 eV and a scattering angle of 2 degrees are presented for alkyl derivatives of H₂O and related compounds. Spectra of H₂O, CH₃OH, CH₃OCH₃, ethylene oxide, CH₃CH₂OH, (CH₃)₂CHOH, (CH₃)₃C C₂H₅OC₂H₅ and tetrahydrofuran are tentatively assigned using derived term values and ionization potentials from photoelectron spectrosc Substituent effects on Rydberg orbital energies are discussed using Taft σ* values.     

Inner-shell excitation of formaldehyde,acetaldehyde and acetone studied by electron impact

Excitation and ionisation of the carbon and oxygen 1s electrons of formaldehyde, acetaldehyde and acetone have been examined by small-angle inelastic scattering of 2.5-keV electrons, with energy resolutions in the range 0.20–0.50 eV FWHM. Features in the electron energy loss spectra below the inner-shell ionisation thresholds have been assigned to transitions to unoccupied valence (π*) and Rydberg orbitals. Broad maxima in the inner-shell continua of all three molecules have been interpreted as resonances associated with transitions to σ*(CO) orbitals. The assignments of the acetaldehyde and acetone spectra have been supported by comparison with those for CH₄ and H₂ CO. The adiabatic first ionisation potential of H₂ NO and H₂ CF have been estimated from the inner-shell spectra of formaldehyde using the equivalent-core analogy.     

Inner shell electron energy loss spectra of the methyl amines and ammonia

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of the methyl amines CH₃NH₂, (CH₃)₂NH and (CH₃)₃N for both the N 1s and C 1s regions. A spectrum of the N 1s region of NH₃ is also presented at higher resolution than previously published data. The C ls spectra are all very similar and the discrete portions may be assigned to Rydberg transitions. However, features attributable to a σ^* shape resonance are observed just above the N 1s and C ls ionization edges. The NH₃ spectrum is ascribed to Rydberg transitions. The N 1s spectra of the methyl amines, however, become increasingly dominated by a σ* resonance in the continuum with increased methylation. The features in the inner-shell spectra are compared with the reported valence-shell optical absorption spectra and support the Rydberg assignment. The inner-shell spectra of (CH₃)₃N and NH₃ are also compared with previously published inner shell electron energy loss spectra of NF₃ and the third row phosphorus analogues PF₃,P(CH₃)₃andPH₃.     

A double-minimum skeletal torsion in 1-silabicyclo[2.2.2]octane by microwave spectroscopy

The 1-silabicyclo[2.2.2]octane molecule HSi(CH₂CH₂)₃CH was investigated by microwave spectroscopy. The observed spectra followed the symmetric-rotor pattern with the unresolved K structures, but were accompanied by many strong vibrational satellites. A series of the prominent satellites was assigned to the excited states of the skeletal torsion. The transition frequencies and the relative intensities which were measured for the satellites were used to determine the double-minimum potential function to the skeletal torsion. The height of the potential hump and the equilibrium torsional angle, which was defined as the SiCCC dihedral angle, were determined to be 606 ± 40 cal/mole and 21.3° ± 1.0°, respectively. The results that the double-minimum nature of the potential function is more pronounced in 1-silabicyclo[2.2.2]octane than in other bicyclo[2.2.2]octane derivatives studied previously are discussed in detail in terms of the internal-rotation potential around the CC and CSi bonds and the strains in the valence angles of the C and Si atoms.     

Electronic spectrum of acetaldehyde: Vibrational analysis of the 182-nm system

The electronic absorption spectra of CH₃CHO, CH₃CDO, CD₃CHO, and CD₃CDO have been obtained in the vacuum ultraviolet region. Vibrational analysis of the 182-nm system was made with the help of wavenumbers from their infrared spectra and also geometries and wavenumbers obtained from ab initio calculations. This system is assigned as a single Rydberg (3s ? n) electronic transition.     

Vacuum ultraviolet absorption spectra of dichlorosilane,dichloromethylsilane and dichlorodimethylsilane

The vapor phase vacuum ultraviolet absorption spectra of dichlorosilane, dichloromethylsilane and dichlorodimethylsilane are reported for the region from 40 000 to 83 000 cm^?1 (250-120 nm). Absorptions of these compounds are assigned as primarily Rydberg excitations of chlorine valence non-bonded electrons. The σ* ← np(SiCl) transition for these compounds is the first observed absorption and is badly overlapped with the first Rydberg absorptions. The first three ionization potentials of dichloromethylsilane were calculated to be 11.47, 11.82, and 12.28 eV using averaged term values and transition energies. The analysis of these spectra revealed that the first p and d molecular Rydberg states appear to be nearly degenerate and that these Rydberg levels are greatly destabilized with methyl substitution. The results of this study support the presence of strong d-p(SiCl) interactions. The strength of this effect is compared in dichlorosilane and dichlorodimethylsilane using an empirical relation.     

Thermal evolution of acetylene and ethylene on Pd(111)

The thermal evolution of acetylene and ethylene and their deuterated counterparts on a palladium (111) surface has been studied by high-resolution electron energy loss spectroscopy in the temperature range 150–500 K. Analysis of the vibrational spectra indicates that chemisorbed acetylene evolves at 300 K in the presence of surface hydrogen to mainly ethylidyne, CCH₃, and a small amount of residual acetylene. Spectra obtained with and without preadsorbed hydrogen provide evidence for a 〉C CH₂ intermediate in the reaction. Chemisorbed ethylene also evolves to ethylidyne after heating from 150 to 300 K but much of the ethylene desorbs. The high temperature (400–500 K) behavior of C₂H₂ and C₂H₄ involves formation of a CH species. Although a small amount of the CH species may be formed from the dehydrogenation of ethylidyne, it is found that carbon-carbon bond scission of acetylene near 400 K is the dominant mechanism in CH formation.     

Microwave spectrum and conformation of thiomorpholine

The microwave spectrum of normal thiomorpholine (CH₂CH₂SCH₂CH₂NH) was investigated within the region 8–40 GHz, and that of N-deuterothiomorpholine (CH₂CH₂SCH₂CH₂ND) within the region 26.5–40 GHz. The observed spectra are due to the chair equatorial conformers. The rotational constants of both isotopic species were determined for the ground states and for two vibrationally excited states. The dipole moment components and quadrupole coupling constants of normal thiomorpholine and the iminohydrogen r_s coordinates were also determined.     

Raman spectra of several layer compounds with charge density waves

Raman scattering studies of the transition metal dichalcogenide layer compounds 1TTaS₂, 1TTaSe₂, 2H-TaSe₂ and 1TVSe₂ are reported. The materials were studied with commensurate and incommensurate charge density waves (CDWs) as well as in the absence of CDWs. Large qualitative changes observed in the Raman spectra are associated with the formation of CDWs and the change from an incommensurate to a commensurate phase.     

He(I) and He(II) photoelectron spectra of some organo-mercury compounds with carbon π-systems

The UV photoelectron spectra of a series of aromatic mercury derivatives {(C₆H₅)₂ Hg, (pCH₃C₆H₄)₂Hg, C₆H₅HgCl, pCH₃C₆H₄HgCl} and of a series of alkynyl mercury derivatives {(CH₃C)₂Hg, ((CCH₃)₃CCC)₂Hg, (ClCC)₂Hg} are reported and discussed. Particular attention is devoted to possible interactions between mercury orbitals and π systems of the ligands. In this respect differences are observed between the two series: in the alkynyl derivatives ligand-field effects are evident on the 5d mercury orbitals, whilst they are not observable in the aromatic compounds.     

Photoelectron and electronic absorption spectra of SCl2, S2Cl2, S2Br2 and (CH3)2S2

Photoelectron and electronic absorption spectra of SCl₂, S₂Cl₂, S₂Br₂, and (CH₃)₂S₂ have been measured and analyzed. Quantum chemical calculations (CNDO/ 2 and MWH (Mulliken-Wolfsberg-Helmholtz) have been carried out and the electronic structures have been described in terms of molecular orbital theory. The variation in differential photoionization cross-section as a function of incident photon energy and results of MO computations are used to identify ionization bands and assign ground state MO configurations. Suggested ground state electronic structures coupled with computed virtual MO's are used to interpret the visible and near-ultraviolet electronic absorption spectra. The low energy excited states are described as molecular states followed by the initial members of Rydberg series. Calculated oscillator strengths for molecular transitions are in good agreement with those observed experimentally. Quantum defects, δ, for the Rydberg states have been calculated from the Rydberg equation using the adiabatic first ionization potential.     

Inner-shell excitation and EXAFS-type phenomena in the chloromethanes

Small angle inelastic scattering of 2.5 keV electrons was used to study the inner-shell excitation of CH₄, CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄ and C₂H₅Cl in the regions of carbon 1s, chlorine 2p and chlorine 2s excitation. Structure observed below the carbon 1s ionization threshold in each molecule is assigned to promotions of a carbon 1s electron to unoccupied valence and Rydberg orbitals. Trends in the distribution of spectral intensities through the series of chloromethane carbon 1s spectra are discussed in terms of the growth of a potential barrier. Broad features are observed in the chlorine 2p continua of CH₂Cl₂, CHCl₃ and CCl₄ and the carbon 1s continuum of CCl₄ which are assigned as the energy loss equivalent of extended X-ray absorption fine structure (EXAFS).     

Proton-NMR study on chemisorption of ethylene on platinum powder

The high-temperature phase of ethylene on surfaces of Pt powder has been studied by proton-NMR in order to decide whether the surface species is the ethylidyne species (CH₃C) proposed by Kesmodel et al. or the multiple-bonded species (CH₂CH) proposed by Demuth. The observed NMR spectrum is not attributable to CH₃-groups on the surfaes, but can be interpreted as the superposition of two signals, one originating from CH₂-groups and the other from CH-groups. In other words, the results suggest that the surface species is the multiple-bonded species.     

丙酮分子的分质量共振多光子电离光谱及多光子电离—离解机理研究

用多光子电离飞行时间质谱法三光子与丙酮分子３ｄ形态和４ｓ态共振的激光波长区域获得了丙酮分子的共振多光子电离分质量多光子电离（ＭＰＩ）光谱和飞行时间质谱，实验观察到的主要产物是ＣＨ３ＣＯ＾＋和ＣＨ＾＋３，还观察到了少量的Ｃ＾＋，ＣＨ＾＋，ＣＨ＾＋２和ＣＨＯ＾＋，在实验的激光波长范围内未见到母体离子，分质量多光子电离光谱具有相似的光谱结构，几个主要谐峰分别对应着（ｎ０，３ｄ）和（ｎ０，４ｓ）里德堡跃迁     

The microwave spectrum and structure of chloromethyl cyclopropane

The microwave spectra of $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁵Cl and $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁷Cl have been observed and lines assigned to the gauche form. The rotational constants in MHz and distortion constants in KHz are: C₃H₅CH₂³⁵Cl, A = 11745.65, B = 2047.274, C = 1886.622, Δ_J = 0.85, Δ_JK = ? 0.9, Δ_K = 44., δ_J = ? 0.099, δ_K = 19.1, C₃H₅CH₂³⁷Cl, A = 11691.61B = 1997.664, C = 1842.823, Δ_J = 0.7, Δ_JK = ? 64.6, Δ_K = 2400, δ_J = 0.19, δ_K = ? 67.     

Surface properties of superparamagnetic iron oxide MR contrast agents: Ferumoxides,ferumoxtran, ferumoxsil

The surface properties of the active ingredients in AMI colloidal, superparamagnetic iron oxide magnetic resonance (MR) contrast agents are described. Scanning electron microscopy/energy dispersive X-ray elemental analyses and diffuse reflectance Fourier transform infrared spectroscopy (FTIR) spectra of ferumoxsil (AMI-121 drug substance) were consistent with the presence of a monolayer of H₂NCH₂CH₂NHCH₂CH₂CH₂Si(O⁻)₃ siloxane monomer or dimer. The X-ray photoelectron spectra (XPS) of ferumoxsil are also consistent with complete coverage of the iron oxide surface with a monolayer of siloxane. The static secondary ion mass spectra (SSIMS) of ferumoxsil showed that the siloxane film is covalently bonded (i.e., SiOFe bonds) to the iron oxide surface. The FTIR of ferumoxides (AMI-25) and Ferumoxtran (AMI-227) showed only adsorbed dextran. The XPS spectra of the dextrancoated colloids showed that Ferumoxtran has a thicker layer of dextran than ferumoxides iron oxide particles (∼5 and ∼3 nm, respectively). The SSIMS spectra of these dextran-coated colloids showed only low mass fragments due to the adsorbed dextran. The nature of the interactions of the dextran coating with the iron oxide surfaces of ferumoxides and Ferumoxtran is discussed.     

Microwave spectrum,structure, dipole moment,and quadrupole coupling constants of isopropylamine

The microwave spectra of (CH₃)₂CHNH₂, (CH₃)₂CHNHD, and (CH₃)₂CHND₂ have been assigned and analyzed. Only c-type, R-branch transitions were identified. The observed spectra correspond to the trans rotamer, as shown by planar moments, the deuterium isotope effect, dipole moment components, and the N quadrupole coupling constants. The CN bond distance is shorter than that observed in methyl amine, as expected, and significantly longer than that in the analogous closed-ring compound cyclopropylamine.     

Collisional transfer between rotational levels of OCS

Steady-state four-level microwave double-resonance experiments are described for pure OCS and OCS diluted with CH₃OH, H₂, and He. For pure OCS, interactions of higher order than first-order dipole-dipole dominate the behavior of some four-level systems, and the rates of ΔJ = 2 quadrupole-type collision-induced transitions are found to be greater than one-half of the ΔJ = 1 dipolar rates. For OCSCH₃OH mixtures, the dipolar rates are significantly enhanced with respect to the pure gas, but ΔJ = 2 transitions are still important. For the mixtures of astrophysical interest, OCSH₂ and OCSHe, all four-level systems show ΔJ = 2 collisional preferences. The ΔJ = 2 transition rates are comparable to those of ΔJ = 1 transitions, and there is evidence that ΔJ = 3 transition rates are substantial.     

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)

The mechanism of ethanol decomposition on the Ni(111) surface has been investigated between 155 and 500 K. The sequence of bond scission steps which occur as ethanol undergoes dissociative reactions on this surface has been deduced using deuterium and ¹³C isotopic labels. Bond activation occurs in the order (1) OH, (2) CH₂ (methylene CH), (3) CC, (4) CH₃ (methyl CH). The products observed are CH₃CHO(g), CH₄(g), CO(g), H₂(g) and surface carbon, C(a). The latter species exhibits a carbidic AES lineshape in the temperature range 450 to 670 K, at which temperature it dissolves into the Ni bulk. Acetaldehyde, CH₃CHO, and methane, CH₄, desorb with the same threshold temperature (260–265 K), and the formation of both of these products is controlled by scission of the methylene CH bond (CH₂ group). The CH₃ group is cleaved from the intermediate surface CH₃CHO species to form CH₃(ads). H₂ exhibits a broad, doublet desorption peak from 300 to 450 K. The carbonoxygen bond in ethanol remains intact and CO ultimately desorbs in a single desorption limited process (T_p = 430 K). A small fraction of CO(a) species undergo exchange with the carbidic surface carbon in a minor process observed above 440 K.