Electronic excitations in phosphorus-containing molecules. I. Inner shell electron energy loss spectra of PH3, P(CH3)3, PF3 and PCL3

Electron energy loss Spectroscopy has been used to obtain the inner shell electronic excitation spectra of PH₃, PF₃, PCl₃ and P(CH₃)₃ in the phosphorus L-shell (P 2p, 2s) region as well as the respective ligand K -shells (F 1s, C 1s) and L-shell (Cl 2p and 2s) regions. The spectra were obtained under small momentum transfer conditions so that dipole-allowed transitions dominate. An impact energy of 2.5 ke V was used and inelastically scattered electrons were detected at a typical scattering angle of about 1°. A dipoleforbidden transition of unusual character is observed at 135.11 eV in the P 2p spectrum of PCl₃. Although optically forbidden, as indicated by its absence in a soft X-ray absorption spectrum, the intensity of this transition rises very rapidly with increase in momentum transfer.     

Inner shell excitation,valence excitation and core ionization in NF3 studied by electron energy-loss and X-ray photoelectron spectroscopies

Electron energy-loss Spectroscopy (EELS) at impact energies of 2.5–3 keV has been used to obtain the electron excitation spectra for the N 1s (K-shell), F 1s (K-shell) and valence shell regions of NF₃. The inner shell spectra were recorded using small angle scattering (?1° ) while the valence shell spectrum was obtained at zero degree scattering angle. The inner shell excitation spectra show a strongly enhanced 1s→ δ^* type transition and continuum features which are typical for molecules with highly electronegative ligands. One of the peaks in an earlier published photoabsorption study of the N 1s region has been shown to be due to a N₂ impurity. The valence shell electron energy-loss spectrum shows a number of transitions which are considered to be mainly due to valence-valence type transitions, with also some evidence of Rydberg structure.The X-ray photoelectron spectra (XPS) of the N 1s and F 1s electrons along with their associated satellite structures have also been recorded using Al Kα (1486.58 eV) radiation. The vertical ionization potentials for the N 1s and F 1s electrons were found to be 414.36 (10) eV and 693.24 (10) eV, respectively. Both spectra exhibit a rich and different satellite structure. These “shake-up” features in the satellite XPS spectra are compared with continuum features of the inner shell electron energy-loss spectra and also with the valence shell spectrum.     

Electronic excitation in phosphorus-containing molecules. II. Inner shell electron energy loss spectra of PF5, OPF3 AND OPCl3

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of PF₅, OPF₃ and OPCl₃ in the P 2p,2s (L-shell) region as well as in the respective ligand K shell (F 1s, O 1s) and L shell (Cl 2p and 2s) regions. The spectra are compared and contrasted with earlier reported spectra obtained on the trivalent phosphorus compounds (PH₃, PCl₃, PF₃ and P(CH₃)₃). The spectra were obtained using an impact energy of 2.5keV and a scattering angle of about 1°. The spectra reported here are typical of molecules with electronegative ligands in that the discrete portions of the spectra show strong transitions to virtual molecular orbitais. In addition, intense features are observed at or just beyond the ionization edge attributable to transitions to trapped inner well states, while broad features further into the continuum can be ascribed to σ^*(P—L) shape-resonances (L = ligand). This resonance assignment was supported by a comparison with the corresponding spectra for PF₃ and PCl₃.     

On the assignment of the carbon K-shell spectra of the methyl halides

Electron energy loss spectra of the methyl halides in the region of carbon K-shell excitation have been obtained at higher resolution than those previously reported. The existence of two electronic transitions between 288 and 290 eV in CH₃F is demonstrated. This result conflicts with a recent SCF calculation which suggests that the σ* (C–F) level in CH₃F is unbound and thus predicts the existence of only one electronic transition in this spectral region. Studies of the carbon K-shell spectra of CH₃Br and CD₃Br demonstrate the vibrational origin of some spectral features. These new results support our earlier tentative assignments for the carbon K-shell spectra of the methyl halides.     

Electron energy loss spectra of the silicon 2p, 2s, carbon 1s and valence shells of tetramethylsilane

Inner shell excitation spectra of tetramethylsilane, (CH₃)₄Si, have been measured in the silicon 2s, 2p (L_I,II,III-shell) and carbon is (K-shell) regions using electron energy-loss spectroscopy at an impact energy of 2.5 keV and a scattering angle of ~1°. The high-resolution valence shell spectrum has also been observed at an impact energy of 3 keV and a zero degree scattering angle. The silicon 2p spectra are compared and contrasted with published photoabsorption spectra of SiF₄, SiH₄, and other related Si-containing molecules with varying ligands.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

X-ray spectroscopic studies of the electronic structure of the oxyanions NO 2−, NO 3− and CO 32−

Using synchrotron radiation for excitation, the K-emission spectra of nitrogen and oxygen in NO ₂^? and NO ₃^?, and of carbon and oxygen in CO ₃^2? were measured. The X-ray spectra together with available photoelectron spectra permit a precise positioning of the occupied orbitals of the anions. The intensities of the X-ray spectra provide information on the atomic orbital composition. In general the agreement between the experimental results and those of MO-calculations is satisfactory; in some cases, however, there are considerable discrepancies.     

A High-Resolution Fourier Transform Infrared Study of the ν3, ν4, and ν5 Bands of Deuterated Formyl Chloride (DCOCl)

High-resolution infrared spectra of the low-lying ν₃, ν₄, and ν₅ fundamentals of the transient molecule DCOCl are reported. These type-A/B hybrid bands have been analyzed in detail, providing extensive rotational assignments for the DCO³⁵Cl and DCO³⁷Cl isotopomers. The ground state constants have been refined by a simultaneous fit of the available microwave data and FTIR combination differences from the three bands. The excited state constants have been determined by fitting assignments over a wide range of J and K_a values. A small perturbation was found at high K_a values in the ν₄ band and determined to be due to a ΔK_a = −2 interaction with the rotational levels of the 6¹ vibrational state.     

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).     

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.     

Microwave spectra of CH314NC and CH315NC in the 3ν8 state

The microwave spectra of methyl isocyanide and its ¹⁵N derivative in the 3ν₈ state have been observed from 40 to 180 GHz. After the assignment by a graphical method, the analysis has been carried out, first by the reuse of analytical formulas and then by the diagonalization of the energy matrix. Many accidental resonances have been shown to occur between the l = ±1 states, and A₁A₂ doublings for K, l = ±3, ±3 have been discovered. A set of constants in the 3ν₈ state is given for each molecule.     

An investigation into allegations of double scattering in the carbon K-shell electron energy loss spectrum of acetylene

In several recent publications (R. G. Cavell and D. A. Allison, J. Chem. Phys., 69 (1978) 159; A. Barth et al., Chem. Phys., 46 (1980) 149) it has been suggested that the feature at 295.6 eV energy loss in the carbon K-shell spectrum of C₂H₂ may arise from double scattering (i.e., collisions of one electron with two acetylene molecules). The pressure-dependence of the carbon K-shell excitation spectrum of C₂H₂ has been examined by inelastic scattering of 2.5-keV electrons to investigate this possibility. The intensity of all features, including that at 295.6 eV, was observed to vary linearly with pressure, indicating that the spectral features arise only from single collisions.     

Argon matrix Raman and infrared spectra of SF5Cl,SF5Br,and S2F10

Infrared and laser-excited Raman spectra of SF₅Cl, SF₅Br, and S₂F₁₀ have been observed in dilute argon matrices and in the solid phase at 8 K. The first vibrational assignment of the SF₅Br molecule and assignments for the ν(SCl), ν(SBr), and ν(SS) modes in SF₅Cl, SF₅Br, and S₂F₁₀ are presented. The chlorine isotopic components of the SCl stretch in SF₅Cl have been resolved. The Raman spectrum of SF₅Br, which has not been reported previously, is discussed.     

Carbon K-shell excitation of C2H2, C2H4, C2H6 and C6H6 by 2.5 keV electron impact

Energy loss spectra of 2.5 keV electrons in the region of the carbon K-edge in C₂H₂, C₂H₄, C₂H₆ and C₆H₆ are report     

The high-resolution infrared spectra of the ν2 and ν3 bands of HOCl

The infrared spectra of the a-type transitions of the ν₂ and ν₃ bands of HO³⁵Cl and HO³⁷Cl have been obtained under high resolution. Line assignments of both bands have been made, and the spectroscopic constants have been obtained for both bands using a Watson Hamiltonian. Lines of the K_a = 5 subband of the ν₂ band of the HO³⁵Cl molecule were found to be slightly shifted by an interaction with the K_a = 4 level of the 2ν₃ vibrational state. The b-type transitions permitted for both bands were too weak to observe. Relative intensities of selected lines of both bands have been measured, and empirical Herman-Wallis factors have been determined.     

Theoretical transition energies,lifetimes and fluorescence yields of multiply ionized silicon

Theoretical X-ray transition energies, lifetimes and partial multiplet fluorescence yields are presented for all spectroscopic terms of electron configurations with a single K-shell vacancy and varying number of electrons in the L-shell and M₁-subshell for multiply-ionized silicon.     

Vibrational spectra of (CD3)2Cd and (CD3)2Zn

The Raman and infrared spectra of (CH₃)₂Cd and (CH₃)₂Zn have been reexamined and are reported along with previously unreported vibrational data for (CD₃)₂Cd and (CD₃)₃Zn. The spectra have been analyzed using the double group $\text{G}{}_{36}\text{2}$, which has led to some changes in assignments made previously. Comparison is also made with a recent study of (CH₃)₂Hg and (CD₃)₂Hg. Fine structure was observed for two of the vibrations of the E_1d symmetry species, arising from internal rotation of the methyl groups. This structure has been analyzed using a recently developed theory for molecules of the freely rotating dimethylacetylene type. Problems which arise in the application of this theory have been pointed out, and it is suggested that some additional consideration of the theory may be necessary.     

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.     

DasK-Röntgenemissionsspektrum des Chlors in freien Molekülen

TheKα andKβ spectra of chlorine in free molecules were studied using a special fluorescence X-ray tube and a high resolving curved crystal spectrograph with photoelectric registration. It was found that the wavelength shifts of ClKα₁ obtained for various gaseous compounds do not show the regularities observed with solid compounds of other 3rd period elements. — TheKβ spectrum consists of discrete lines the most intense of which result from transitions of the lonely pair electrons of the chlorine atoms. The spectra of HCl, Cl₂ and CH₃Cl can be explained using optical and betaspectroscopical data and MO calculations. The general structure of ClKβ of organic compounds seems to be determined by the hybridisation type of the carbon atoms bound to the chlorine atoms. Evidence is found for a contribution of molecular vibrational energy to the energies of the X-ray transitions.     

3.508 μ-HeXe-laser line absorption by CH3COOCH3, CH3, and NO2 and infrared emission at 6.89 μ by CH3COOCH3 and CH3 at elevated temperatures

Shock-tube HeXe-laser absorption data at ω_L=2850.633 cm^-1 for CH₃COOCH₃ at 757≤T, °K≤1344, NO₂at 412≤T, °K≤1859, andCH₃at 1283≤T, °K≤1562 are presented. Approximate models are used for the effective spectral absorption coefficient of vibration-rotation lines for analytical representations of the results around atmospheric pressures. For CH₃COOCH₃, an equivalent Voigt-profile for an isolated line was adopted in order to account for a dependence on total pressure of the laser absorption coefficient. Shock-tube emission data at λ=6.890 μ(Δλ=0.197μ) forCH₃COOCH₃at 814≤T, °K≤1651 and for CH₃at 1377≤T, °K≤1562 in the v₄-fundamental of the H-bond bending mode of the CH₃-group are well described at atmospheric pressures by approximations of just-overlapping-line models for polyatomic molecules. The adopted models are useful for concentration-time history measurements of methyl acetate, nitrogen dioxide, and methyl radicals behind shock waves.