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The valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine have been studied both experimentally and theoretically. Synchrotron radiation has been employed to record angle resolved photoelectron spectra in the photon energy range 20-100 eV, and these have enabled anisotropy parameters and branching ratios to be derived. The experimental results have been compared with theoretical predictions obtained using the continuum multiple scattering Xα approach. This comparison shows that the anisotropy parameter associated with the nominally chlorine lone-pair orbital lying in the molecular plane is strongly affected by the atomic Cooper minimum. In contrast, the photoionization dynamics of the second lone-pair orbital, orientated perpendicular to the molecular plane, seem relatively unaffected by this atomic phenomenon. The outer valence ionization has been studied theoretically using the third-order algebraic-diagrammatic construction (ADC(3)) approximation scheme for the one-particle Green's function, the outer valence Green's function method, and the equation-of-motion (EOM) coupled cluster (CC) theory at the level of the EOM-IP-CCSD and EOM-EE-CC3 models. The convergence of the results to the complete basis set limit has been investigated. The ADC(3) method has been employed to compute the complete valence shell ionization spectra of 2-chloropyridine and 3-chloropyridine. The relaxation mechanism for ionization of the nitrogen σ-type lone-pair orbital (σN LP) has been found to be different to that for the corresponding chlorine lone-pair (σCl LP). For the σN LP orbital, π-π* excitations play the main role in the screening of the lone-pair hole. In contrast, excitations localized at the chlorine site involving the chlorine πCl LP lone-pair and the Cl 4p Rydberg orbital are the most important for the σCl LP orbital. The calculated photoelectron spectra have allowed assignments to be proposed for most of the structure observed in the experimental spectra. The theoretical work also highlights the formation of satellite states, due to the breakdown of the single particle model of ionization, in the inner valence region. [ABSTRACT FROM AUTHOR]

The valence shell ionization spectrum of pyridine was studied using the third-order algebraicdiagrammatic construction approximation scheme for the one-particle Green's function and the outer-valence Green's function method. The results were used to interpret angle resolved photoelectron spectra recorded with synchrotron radiation in the photon energy range of 17-120 eV. The lowest four states of the pyridine radical cation, namely, 2A2(1a2-1), 2A1(7a1-1), 2B1(2b1-1) and 2B2(5b2-1), were studied in detail using various high-level electronic structure calculation methods. The vertical ionization energies were established using the equation-of-motion coupled-cluster approach with single, double and triple excitations (EOM-IP-CCSDT) and the complete basis set extrapolation technique. Further interpretation of the electronic structure results was accomplished using Dyson orbitals, electron density difference plots and a second-order perturbation theory treatment for the relaxation energy. Strong orbital relaxation and electron correlation effects were shown to accompany ionization of the 7a1 orbital, which formally represents the nonbonding ó-type nitrogen lone-pair (nó) orbital. The theoretical work establishes the important roles of the л-system (л-л* excitations) in the screening of the nó-hole and of the relaxation of the molecular orbitals in the formation of the 7a1(nó) 1 state. Equilibrium geometric parameters were computed using the MP2 (second-order Møller-Plesset perturbation theory) and CCSD methods and the harmonic vibrational frequencies were obtained at the MP2 level of theory for the lowest three cation states. The results were used to estimate the adiabatic 0-0 ionization energies, which were then compared to the available experimental and theoretical data. Photoelectron anisotropy parameters and photoionization partial cross sections, derived from the experimental spectra, were compared to predictions obtained with the continuum multiple scattering approach. [ABSTRACT FROM AUTHOR]

Angle resolved photoelectron spectra of the X ²B1, Ã ²A2, B ²B1, and C ²B1 states of bromobenzene have been recorded over the excitation range 20.5-94 eV using linearly polarized synchrotron radiation. The photoelectron anisotropy parameters and electronic branching ratios derived from these spectra have been compared to theoretical predictions obtained with the continuum multiple scattering approach. This comparison shows that ionization from the 8b2 orbital and, to a lesser extent, the 4b1 orbital is influenced by the Cooper minimum associated with the bromine atom. The 8b2 and 4b1 orbitals are nominally bromine lone-pairs, but the latter orbital interacts strongly with the p-orbitals in the benzene ring and this leads to a reduced atomic character. Simulations of the X ²B1, B ²B2, and C ²B1 state photoelectron bands have enabled most of the vibrational structures appearing in the experimental spectra to be assigned. Many of the photoelectron peaks exhibit an asymmetric shape with a tail towards low binding energy. This asymmetry has been examined in the simulations of the vibrationally unexcited peak, due mainly to the adiabatic transition, in the X ²B1 state photoelectron band. The simulations show that the asymmetric profile arises from hot-band transitions. The inclusion of transitions originating from thermally populated levels results in a satisfactory agreement between the experimental and simulated peak shapes. [ABSTRACT FROM AUTHOR]

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n = 5 manifolds of excited states of larger molecules. [ABSTRACT FROM AUTHOR]

The absolute photoabsorption cross section of propyne was recorded between 62 000 and 88 000 cm−1 by using the vacuum-ultraviolet, Fourier-transform spectrometer at the Synchrotron Soleil. This cross section spans the region including the lowest Rydberg bands and extends above the Franck-Condon envelope for ionization to the ground electronic state of the propyne cation, X ̃+. Room-temperature spectra were recorded in a flowing cell at 0.9 cm−1 resolution, and jet-cooled spectra were recorded at 1.8 cm−1 resolution and a rotational temperature of ∼100 K. The reduced widths of the rotational band envelopes in the latter spectra reveal new structure and simplify a number of assignments. Although nf Rydberg series have not been assigned previously in the photoabsorption spectrum of propyne, arguments are presented for their potential importance, and the assignment of one nf series is proposed. As expected from previous photoelectron spectra, Rydberg series are also observed above the adiabatic ionization threshold that converge to the v3+ = 1 and 2 levels of the C≡C stretching vibration. [ABSTRACT FROM AUTHOR]

A c(2 × 4) LEED pattern is observed for methylidyne (CH) chemisorbed on Pt{110}(1 × 2) at a saturation coverage of 0.25 ML. Density functional calculations reveal that methylidyne is preferentially adsorbed in the fcc three-fold hollow site on the {111} microfacet of the reconstructed surface. A structure for the ordered overlayer is thus proposed, and both through-metal and through-space interactions are considered as possible causes for this unexpected long-range coherence. We argue that entropic effects may be implicated. [ABSTRACT FROM AUTHOR]

Hydrogen-deuterium exchange in adsorbed methylidyne, CH[sub a], on Pt{110}-(1 × 2) has been studied for the first time using supersonic D[sub 2]/H[sub 2] molecular beams, which provides new insights into the reversible hydrogenation of adsorbed hydrocarbon fragments. The exchange reaction is extremely facile at surface temperatures of 350-450 K and proceeds via a Langmuir-Hinshelwood reaction between D[sub a] and a CH[sub a] fragment to produce gas phase H[sub 2] and HD. The CD[sub a] + H[sub a] (i.e., reverse) reaction was also studied and was found to proceed more slowly. Both exchange reactions were successfully modeled and the difference in reaction rates is explained using zero point energy differences alone. Finally, we demonstrate that with high incident D[sub 2] fluxes CH[sub a] can be completely deuterated to produce gaseous CHD[sub 3] and CD[sub 4]. © 2001 American Institute of Physics. [DOI: 10.1063/1.1410387]. [ABSTRACT FROM AUTHOR]

Room temperature and rotationally cooled relative photoionization cross sections for H2O and D2O were determined in the wavelength region 650–990 Å with a wavelength resolution of 0.06–0.11 Å (∼7–12 cm-1 ); the spectra were normalized to the absolute photoionization cross sections determined by Katayama et al. [D. H. Katayama, R. E. Huffman, and C. L. O’Bryan, J. Chem. Phys. 59, 4309 (1973)] with lower resolution. A rotational analysis of the Π subbands in the (0,6,0) and (0,8,0) bands of the (A 2A1)3db11B1←X1A1 Rydberg transition determined the symmetry of the upper state; in addition, the series was extended to higher principal quantum numbers. The analysis of these and other bands was made difficult both by the large natural linewidths of the rotational transitions and by the absence of transitions to rotational levels with N’>=3. [ABSTRACT FROM AUTHOR]

The influence of vibronic coupling on the outer valence ionic states of cis-dichloroethene has been investigated by recording photoelectron spectra over the excitation range 19–90 eV using plane polarized synchrotron radiation, for two polarization orientations. The photoelectron anisotropy parameters and electronic state branching ratios derived from these spectra have been compared to theoretical predictions obtained with the continuum multiple scattering approach. This comparison shows that the photoionization dynamics of the à 2B2, B ̃ 2A1, C ̃ 2A2, and D ̃ 2B1 states, all of which are formed through the ejection of an electron from a nominally chlorine lone-pair orbital, exhibit distinct evidence of the Cooper minimum associated with the halogen atom. While retaining a high degree of atomic character, these orbital ionizations nevertheless display clear distinctions. Simulations, assuming the validity of the Born-Oppenheimer and the Franck-Condon approximations, of the X ̃ 2B1, à 2B2, and D ̃ 2B1 state photoelectron bands have allowed some of the vibrational structure observed in the experimental spectra to be assigned. The simulations provide a very satisfactory interpretation for the X ̃ 2B1 state band but appear less successful for the à 2B2 and D ̃ 2B1 states, with irregularities appearing in both. The B ̃ 2A1 and C ̃ 2A2 state photoelectron bands exhibit very diffuse and erratic profiles that cannot be reproduced at this level. Photoelectron anisotropy parameters, β, have been evaluated as a function of binding energy across the studied photon energy range. There is a clear step change in the β values of the à 2B2 band at the onset of the perturbed peak intensities, with β evidently adopting the value of the B ̃ 2A1 band β. The D ̃ 2B1 band β values also display an unexpected vibrational level dependence, contradicting Franck-Condon expectations. These various behaviors are inferred to be a consequence of vibronic coupling in this system. [ABSTRACT FROM AUTHOR]

We present a comparison of the photoionization dynamics of the 4d shell of XeF2 from threshold to 250 eV to those of the prototypical 4d shell of atomic Xe. The new experimental data include spin–orbit and ligand-field-resolved partial cross sections, photoelectron angular distributions, branching fractions, and lifetime widths for the 4d-hole states. The spin–orbit branching fractions and angular distributions are remarkably similar to the corresponding distributions from atomic Xe across a broad energy interval that includes both the intense shape resonance in the f continuum and a Cooper minimum in the same channel. The angular distributions and branching fractions are also in reasonably good agreement with our first-principles theoretical calculations on XeF2. Data are also presented on the lifetime widths of the substate-resolved 4d-hole states of XeF2. While the trends in the widths are similar to those in the earlier experimental and theoretical work, the linewidths are considerably smaller than in the previous measurements, which may require some reinterpretation of the decay mechanism. Finally, we present new data and an analysis of the Auger electron spectra for ionization above the 4d thresholds and resonant Auger spectra for several pre-edge features. [ABSTRACT FROM AUTHOR]

Linearly polarized synchrotron radiation has been used to record polarization dependent valence shell photoelectron spectra of imidazole in the photon energy range 21–100 eV. These have allowed the photoelectron angular distributions, as characterized by the anisotropy parameter β, and the electronic state intensity branching ratios to be determined. Complementing these experimental data, theoretical photoionization partial cross sections and β-parameters have been calculated for the outer valence shell orbitals. The assignment of the structure appearing in the experimental photoelectron spectra has been guided by vertical ionization energies and spectral intensities calculated by various theoretical methods that incorporate electron correlation and orbital relaxation. Strong orbital relaxation effects have been found for the 15a′, nitrogen lone-pair orbital. The calculations also predict that configuration mixing leads to the formation of several low-lying satellite states. The vibrational structure associated with ionization out of a particular orbital has been simulated within the Franck–Condon model using harmonic vibrational modes. The adiabatic approximation appears to be valid for the X2A″ state, with the β-parameter for this state being independent of the level of vibrational excitation. However, for all the other outer valence ionic states, a disparity occurs between the observed and the simulated vibrational structure, and the measured β-parameters are at variance with the behavior expected at the level of the Franck–Condon approximation. These inconsistencies suggest that the excited electronic states may be interacting vibronically such that the nuclear dynamics occur over coupled potential energy surfaces. [ABSTRACT FROM AUTHOR]

The valence-shell ionization spectrum of bromobenzene, as a representative halogen substituted aromatic, was studied using the non-Dyson third-order algebraic-diagrammatic construction [nDADC(3)] approximation for the electron propagator. This method, also referred to as IP-ADC(3), was implemented as a part of the Q-Chem program and enables large-scale calculations of the ionization spectra, where the computational effort scales as n5 with respect to the number of molecular orbitals n. The IP-ADC(3) scheme is ideally suited for investigating low-lying ionization transitions, so fresh insight could be gained into the cationic state manifold of bromobenzene. In particular, the present IP-ADC(3) calculations with the cc-pVTZ basis reveal a whole class of low-lying low-intensity two-hole-one-particle (2h-1p) doublet and quartet states, which are relevant to various photoionization processes. The good qualitative agreement between the theoretical spectral profile for the valence-shell ionization transitions generated with the smaller cc-pVDZ basis set and the experimental photoelectron spectrum measured at a photon energy of 80 eV on the PLÉIADES beamline at the Soleil synchrotron radiation source allowed all the main features to be assigned. Some theoretical aspects of the ionization energy calculations concerning the use of various approximation schemes and basis sets are discussed. [ABSTRACT FROM AUTHOR]

The C 1s ionization spectrum of CH3I has been studied both experimentally and theoretically. Synchrotron radiation has been employed to record polarization dependent photoelectron spectra at a photon energy of 614 eV. These spectra encompass the main-line due to the C 1s single-hole state and the peaks associated with the shake-up satellites. Vertical ionization energies and relative photoelectron intensities have been computed using the fourth-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function and the 6-311++G** basis set. The theoretical spectrum derived from these calculations agrees qualitatively with the experimental results, thereby allowing the principal spectral features to be assigned. According to our calculations, two 2A1 shake-up states of the C 1s−1 σCI → σ CI * type with singlet and triplet intermediate coupling of the electron spins (S′ = 0, 1) play an important role in the spectrum and contribute significantly to the overall intensity. Both of these states are expected to have dissociative diabatic potential energy surfaces with respect to the C–I separation. Whereas the upper of these states perturbs the manifold of Rydberg states, the lower state forms a band which is characterized by a strongly increased width. Our results indicate that the lowest shake-up peak with significant spectral intensity is due to the pair (S′ = 0, 1) of 2E (C 1s−1 I 5p → σ CI * ) states. We predict that these 2E states acquire photoelectron intensity due to spin-orbit interaction. Such interactions play an important role here due to the involvement of the I 5p orbitals. [ABSTRACT FROM AUTHOR]

The valence shell photoelectron spectrum of cis-dichloroethene has been studied both experimentally and theoretically. Photoelectron spectra have been recorded with horizontally and vertically plane polarized synchrotron radiation, thereby allowing the anisotropy parameters, characterizing the angular distributions, to be determined. The third-order algebraic-diagrammatic construction approximation scheme for the one-particle Green’s function has been employed to compute the complete valence shell ionization spectrum. In addition, the vertical ionization energies have been calculated using the outer valence Green’s function (OVGF) method and the equation-of-motion coupled-cluster, with single and double substitutions for calculating ionization potentials (EOM-IP-CCSD) model. The theoretical results have enabled assignments to be proposed for most of the structure observed in the experimental spectra, including the inner-valence regions dominated by satellite states. The linear vibronic coupling model has been employed to study the vibrational structure of the lowest photoelectron bands, using parameters obtained from ab initio calculations. The ground state optimized geometries and vibrational frequencies have been computed at the level of the second-order Møller-Plesset perturbation theory, and the dependence of the ionization energies on the nuclear configuration has been evaluated using the OVGF method. While the adiabatic approximation holds for the X ̃ 2B1 state photoelectron band, the A ̃ 2B2, B ̃ 2A1, and C ̃ 2A2 states interact vibronically and form a complex photoelectron band system with four distinct maxima. The D ̃ 2B1 and E ̃ 2B2 states also interact vibronically with each other. The potential energy surface of the D ̃ 2B1 state is predicted to have a double-minimum shape with respect to the out-of-plane a2 deformations of the molecular structure. The single photoelectron band resulting from this interaction is characterized by a highly irregular structure, reflecting the non-adiabatic nuclear dynamics occurring on the two coupled potential energy surfaces forming a conical intersection close to the minimum of the E ̃ 2B2 state. [ABSTRACT FROM AUTHOR]

The single-photon, photoelectron-photoion coincidence spectrum of N2 has been recorded at high (~1.5 cm-1) resolution in the region between the N2+ X ²Σg+, v+ = 0 and 1 ionization thresholds by using a double-imaging spectrometer and intense vacuum-ultraviolet light from the Synchrotron SOLEIL. This approach provides the relative photoionization cross section, the photoelectron energy distribution, and the photoelectron angular distribution as a function of photon energy. The region of interest contains autoionizing valence states, vibrationally autoionizing Rydberg states converging to vibrationally excited levels of the N2+ X ²Σg+ ground state, and electronically autoionizing states converging to the N2+A ²Π and B ²Σu+ states. The wavelength resolution is sufficient to resolve rotational structure in the autoionizing states, but the electron energy resolution is insufficient to resolve rotational structure in the photoion spectrum. A simplified approach based on multichannel quantum defect theory is used to predict the photoelectron angular distribution parameters, β, and the results are in reasonably good agreement with experiment. [ABSTRACT FROM AUTHOR]

The nonradiative decay channels of the valence electronic states of the gas-phase tetrahedral ions CF+4, SiF+4, CCl+4, SiCl+4, and GeCl+4 have been studied in the range 35–100 nm by a novel form of photoionization mass spectrometry. Tunable vacuum UV radiation from a synchrotron source ionizes the parent neutral molecule, and electrons and ions are detected by the photoelectron–photoion coincidence technique. The experiment is repeated continuously as a function of photon energy, and a three-dimensional histogram of photon energy versus ion time of flight versus coincidence count rate is produced. By taking cuts through this histogram, photoionization curves for the different fragment ions can be extracted. The appearance energies of the fragment ions (e.g., CF+2 from CF4, CCl+ from CCl4) occur at the adiabatic ionization potential of an electronic state of the parent ion, and not at the thermodynamic appearance energy of that ion. Attempts to measure the kinetic-energy releases in the fragmentation pathways have only been partially successful. The results are complementary to those of recent experiments to probe the radiative decay of these electronic states of MX+4 [M=C, Si, Ge; X=F, Cl] [J. Chem. Phys. 89, 2675 (1988); 89, 2683 (1988)], where the C 2T2 and D 2A1 third and fourth excited electronic states can show radiative decay to a surprising degree. The decay dynamics of the C and D states of MX+4 are reviewed. In general, the fluorides show different behavior to the analogous chlorides, and the carbon species behaves differently to the corresponding silicon or germanium species. [ABSTRACT FROM AUTHOR]