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Background European canker, caused by Neonectria ditissima, is a disease of worldwide importance in apple production, yet knowledge about it is limited, highly regional and sometimes contradictory. This is an obstacle to successful disease management. Key aspects for Northern Europe are reviewed, based on research results from Northern Germany and Norway and on international literature data. Main topics Trunk cankers developing on young trees within the first 1–3 seasons of explanting can often be traced back to latent infections initiated in the nurseries. The most important nursery infection is a lateral canker on the main trunk of ‘knip’ trees, which are the standard tree type in Northern Europe. In strongly affected batches, up to 25% of trees have to be uprooted after the first growing season due to such trunk cankers. The establishment and maintenance of healthy orchards requires clean nursery material, especially in the case of susceptible cultivars. In Northern Germany, infections within commercial orchards most often proceed through wounds caused by fruit picking or leaf fall in autumn, as shown by the appearance of cankers in the following spring and by the high efficacy of fungicide treatments at leaf fall. Ascospores, commonly thought to be relevant for long-distance spread of infections, are not released until the end of leaf fall even in wet autumn seasons in Northern Germany. Therefore, their role in the disease remains unclear. Strong nitrogen-induced vegetative growth favours apple canker. In field trials conducted under conditions of current commercial practices, autumnal sprays with copper hydroxide or copper oxide were consistently more efficacious than copper oxychloride or captan in preventing new infections. Conclusions Restricted fertilisation and other measures to curb excessive vegetative growth during the first few years of an orchard, repeated canker pruning and well-timed treatments with effective fungicides in autumn are essential for IPM of apple canker. Nonetheless, canker remains capable of severely impairing the commercial success of susceptible cultivars in regions with wet climates even if all available measures are taken. This opens up long-term perspectives for the breeding of more resistant cultivars.

Access to accurate reference data is a prerequisite in order to translate chemical shifts to an absolute scale for inner-shell ionization energies. Calibration standards for oxygen 1s (O 1s) ionization energies are less well established than, for instance, for carbon 1s. To improve upon this situation, adiabatic and vertical O 1s ionization energies for gaseous carbon dioxide (CO2) are critically reviewed and used to establish the most accurate values currently available: 541.085(17) and 541.253(17) eV, respectively. Combining these with new precise measurements of shifts in O 1s ionization energies for H2O, CO, and O2 allows us to establish equally accurate absolute ionization energies for these molecules as for CO2. The resulting adiabatic and vertical energies are 539.728(17) and 539.827(17) eV for H2O, 542.439(17) and 542.495(17) eV for CO, 543.285(17) and 543.294(17) eV for O2 (4Σ final state), and 544.338(17) and 544.423(17) eV for O2 (2Σ final state). It is proposed that O 1s in CO2 be adopted as a standard of higher precedence, and that H2O, CO, and O2 be used also. The O 1s ionization energies in these molecules occur in the range 540–543 eV. These proposed standards should provide optimal internal calibration for a wide range of oxygen-containing compounds. publishedVersion

International audience; We demonstrate that the possibility of monitoring relative photoionization cross sections over a large photon energy range allows us to study and disentangle shake processes and intramolecular inelastic scattering effects. In this gas-phase study, relative intensities of the carbon 1s photoelectron lines from chemically inequivalent carbon atoms in the same molecule have been measured as a function of the incident photon energy in the range of 300–6000 eV. We present relative cross sections for the chemically shifted carbon 1s lines in the photoelectron spectra of ethyl trifluoroacetate (the “ESCA” molecule). The results are compared with those of methyl trifluoroacetate and S-ethyl trifluorothioacetate as well as a series of chloro-substituted ethanes and 2-butyne. In the soft X-ray energy range, the cross sections show an extended X-ray absorption fine structure type of wiggles, as was previously observed for a series of chloroethanes. The oscillations are damped in the hard X-ray energy range, but deviations of cross-section ratios from stoichiometry persist, even at high energies. The current findings are supported by theoretical calculations based on a multiple scattering model. The use of soft and tender X-rays provides a more complete picture of the dominant processes accompanying photoionization. Such processes reduce the main photoelectron line intensities by 20–60%. Using both energy ranges enabled us to discern the process of intramolecular inelastic scattering of the outgoing electron, whose significance is otherwise difficult to assess for isolated molecules. This effect relates to the notion of the inelastic mean free path commonly used in photoemission studies of clusters and condensed matter.

Sweet cherry fruit delivered at three packinghouses over two years in southern Norway was assessed for postharvest fungal decay after being graded in a line with water containing 2 ppm chlorine, in comparison with non-graded fruit. Assessment of decay was carried out after cold storage of the fruit for ten days at 2°C, followed by two days at 20°C. In mean of all assessments, there was no difference in total decay after storage between fruit graded in a water line or non-graded fruit, however, the first year there was a higher total incidence of fruit decay on water-graded fruit after storage. The grading-water was not changed during the day, but time of grading during the day did not seem to influence the amount of decay. Mucor rot and grey mould accounted for 80 and 19%, respectively, of the decay averaged for all assessments, and there was no significant difference in decay of the two diseases if graded in water or not. For blue mould and brown rot, the incidence was lower in water graded fruit, while it was the opposite for Cladosporium rot. On average, fruit decaying fungi developed on PDA from 57 and 17% of water samples from grading lines in the two years, respectively. On pieces with filter paper wetted in different locations of the grading line, 87% contained fruit decaying fungi when placed on PDA, and Mucor sp. was the most prevalent pathogen. Fruit cooled in a hydro-cooler containing either 2, 10 or 50 ppm chlorine, all reduced decay with about 75% compared to non-chlorinated water. Although the grading water may contain spores of pathogenic fungi, the present results indicated that water containing 2 ppm chlorine does not significantly increase fruit decay. Thus, only a slight chlorination of grading water may be sufficient to reduce postharvest contamination.

“Substituent effects” is an important and useful concept in organic chemistry. Although there are many approaches to parametrizing the electronic and steric effects of substituents, the physical basis for the parameters is often unclear. The purpose of the present work is to explore the properties of chemical shifts in carbon 1s energies as a well-defined basis for characterizing substituents to an ethylene C═C moiety. To this end, high-resolution carbon 1s photoelectron spectra of six chloro-substituted ethenes and seven chloro-substituted propenes have been measured in the gas phase. Site-specific adiabatic ionization energies have been determined from the spectra using theoretical ab initio calculations to predict the vibrational structures. For two molecules, 3-chloropropene and 2,3-dichloropropene, the spectral analyses give quantitative results for the conformer populations. The observed shifts have been analyzed in terms of initial-state (potential) and relaxation effects, and charge relaxation has also been analyzed by means of natural resonance theory. On the basis of core-level spectroscopy and models, chlorine, methyl, and chloromethyl have been characterized in terms of their effect on the carbon to which they are attached (α site) as well as the neighboring sp2 carbon (β site). The derived spectroscopic substituent parameters are characterized by both inductive (electronegativity) effects and the ability of each substituent to engage in electron delocalization via the π system. Moreover, the adopted approach is extended to include substituent–substituent interaction parameters. publishedVersion

Electron attenuation due to inelastic and elastic scattering in condensed media can often be described in terms of the effective attenuation length (EAL) of the electron. The EAL is thus an important parameter for describing electron transport processes as exemplified by dissipation of energy following radiolysis. Focusing on electrons at low electron kinetic energies (10-40 eV) in condensed argon, we determine EAL from x-ray photoelectron spectra of argon nanoparticles and compare to values obtained from valence ionization in thin argon films as well as from gas-phase electron-scattering data. EAL determined from argon clusters shows variation with cluster size. Moreover, the values are significantly lower than those obtained in valence-ionization studies and from scattering data. Our results corroborate recent x-ray photoelectron spectroscopy-based determination of EALs of water showing large differences to the EALs determined by other methods in amorphous ice at low kinetic energies of the photoelectron [Y.-I. Suzuki, K. Nishizawa, N. Kurahashi, and T. Suzuki, Phys. Rev. E 90, 010302 (2014)PLEEE81539-375510.1103/PhysRevE.90.010302], underlining that care must be taken when using EAL values from other sources for core-level electrons.

Synopsis We demonstrate that the possibility of monitoring relative photoionization cross sections over a large photon energy range extending to hard x-rays allows studying and disentangling shake processes and intramolecular inelastic scattering effects. An “EXAFS”-type of oscillatory behaviour of the relative C 1s cross sections is observed in a wide photon energy range up to 1 keV due to multiple intramolecular elastic scattering of the photoelectron. These effects are also present in solids and constitute a significant part of all elastic and inelastic scattering effects occurring in solids.

International audience; A method for spectroscopic characterization of free ionic clusters and nanoparticles utilizing X-ray synchrotron radiation is presented. We demonstrate that size-selected ammonium bisulphate cluster ions, NH4+(NH4HSO4)(n), captured in a linear ion trap, exhibit well-defined core-level absorption edges in the reconstructed fragment-ion abundance spectra. In addition to the specific photo-fragmentation pathways observed at the N1s-, O1s- and S2p-edges, dissociation also occurs as a consequence of clusters colliding with helium present as buffer gas in the ion trap. Separate off-beam experiments were conducted to establish the activation kinetics of these collision induced dissociation processes. Furthermore, it is demonstrated that the electrons released upon photoionization of background helium are too few in number to produce multiply charged cluster ions, and thereby induce fragmentation of the salt clusters, to any significant degree. The mechanisms for photon absorption and subsequent cluster fragmentation are analysed and discussed. In addition to its inherent element specificity, the method holds promise for cluster structure elucidation resulting from the sensitivity of the near edge absorption structure to the local chemical environment of the excited atom.

We have investigated the metal–ligand bond energies in C2H4–Pt(PH3)2 and C60–Pt(PH3)2 by means of ab initio correlated methods (MP2, MP4(SDQ), MP4, QCISD, CCSD and CCSD(T)) in conjunction with large basis sets. For D e (C2H4–Pt(PH3)2), an accurate value of 17.2 kcal/mol is established at the CCSD(T) level of theory. Due to the size of the system, the bond energy for the Buckminsterfullerene system was explored in terms of a sequence of model systems of increasing size, providing a D e estimate of 28.2 kcal/mol at the ONIOM(CCSD(T)/C14H8:MP2/C60) level of theory. The performance of a range of high-end density functionals (with and without dispersion) is evaluated for these systems by comparison to the best ab initio results. Among these, we find density functionals BLYP and B3LYP, augmented by Grimme’s D3 dispersion correction (to give the corresponding DFT-D methods), to provide good and consistent agreement with our best estimates. Next, DFT-optimised structures for C2H4–Pt(PPh3)2 and C60–Pt(PPh3)2 are p...

The carbon 1s photoelectron spectra of a series of aliphatic alkynes and alkenes that have the possibility of possessing two or more conformers have been recorded with high resolution. The two conformers of 2-hexyne and 4-methyl-1-pentyne, anti and gauche, have been identified and quantified from an analysis of their carbon 1s photoelectron spectra, yielding 30 ± 5% and 70 ± 6% anti conformers, respectively. In the case of 1-hexyne, the photoelectron spectrum is shown to provide partial information on the distribution of conformers. Central to these analyses is a pronounced ability of the C1s photoemission process to distinguish between conformers that display weak γ-CH/π hydrogen bonding and those that do not. For the corresponding alkene analogs, similar analyses of their C1s photoelectron spectra do not lead to conclusive information on the conformational equilibria, mainly because of significantly smaller chemical shifts and higher number of conformers compared with the alkynes.

Electrophilic addition to multiple carbon-carbon bonds has been investigated for a series of twelve aliphatic and aromatic alkenes and the corresponding alkynes. For all molecules, enthalpies of protonation and activation energies for HCl addition across the multiple bonds have been calculated. Considering the protonation process as a cationic limiting case of electrophilic addition, the sets of protonation enthalpies and gas-phase activation energies allow for direct comparison between double- and triple-bond reactivities in both ionic and dipolar electrophilic reactions. The results from these model reactions show that the alkenes have similar or slightly lower enthalpies of protonation, but have consistently lower activation energies than do the alkynes. These findings are compared with results from high resolution carbon 1s photoelectron spectra measured in the gas phase, where the contribution from carbons of the unsaturated bonds are identified. Linear correlations are found for both protonation and activation energies as functions of carbon 1s energies. However, there are deviations from the lines that reflect differences between the three processes. Finally, substituent effects for alkenes and alkynes are compared using both activation and carbon 1s ionization energies.

Molecular LiCl and Li2Cl2 have been studied in the vapor phase with valence photoelectron and photoelectron-photoion coincidence spectroscopies. These two techniques determine the binding energies in fundamentally different ways. Binding energies obtained from photoelectron spectra are usually taken as the vertical ionization energies of the corresponding electronic states. In cases with several overlapping bands, corresponding to different electronic states, the coincidence measurement can separate the bands if the respective final states fragment differently. This applies well to the monomer case. To facilitate the determination of state-specific ionization energies in the dimeric molecule, a theoretical Franck-Condon analysis has been carried out. Moreover, ab initio coupled-cluster and density-functional-theory calculations have been used to analyze the fragmentation pattern based on asymptotic dissociation energies. The fragmentation pattern is largely common to all the accessible valence-ionized states of the chiller, consistent with rapid conversion to the ionic ground state before fragmentation. However, the highest-lying state of Li2Cl2+, (2)A(g). shows enhanced propensity for Li+ as dissociation product. (C) 2012 Elsevier B.V. All rights reserved. (Less)

The C is photoelectron spectrum of ethyl trifluoroacetate (CF3-CO-O-CH2-CH3), also known as the 'ESCA molecule', is the most illustrative showcase of chemical shifts in photoelectron spectroscopy. ...

Construction of accurate lineshape models for chlorosubstituted hydrocarbons is challenging. In this account the problem has been investigated thoroughly for the chloromethane series, CH4−nCln, n = 1–4, using high-resolution experimental data and extensive theoretical calculations. The C Cl bond contraction following ionization is a key parameter for a quantitative description of the vibrational excitation for all four molecules. We determine this quantity accurately for the title molecules and also propose approximate approaches that may applied to larger molecules. Having developed accurate vibrational lineshape models as well as reliable estimates of the instrumental broadening in each case, the carbon 1s hole lifetime broadening is determined from a fit to the experimental spectrum for each molecule. The resulting values for the lifetime broadening are 88 ± 5 meV for CH3Cl, 80 ± 5 meV for CH2Cl2, 74 ± 5 meV for CHCl3 and 62 ± 5 meV for CCl4. The lifetime widths decrease systematically with the number of chlorine substituents and correlate excellently with the valence occupancy of the core-ionized carbon. This indicates that the one-center model for Auger decay of the core hole is valid for the present series of molecules.

Free neutral CO2 clusters were produced by adiabatic expansion and characterized by carbon 1s (C1s) photoelectron spectroscopy using synchrotron radiation. The shift in C1s ionization energy (IE) between the cluster and the monomer, i.e., ΔIE = IE(cluster) – IE(monomer), was found to vary systematically with the experimental conditions. A functional relationship is established between the mean cluster size in the beam, ⟨N⟩, and ΔIE, in good agreement with theoretical calculations of shifts in ionization energy for model clusters. This makes it possible to use core-level photoelectron spectroscopy to monitor the mean cluster size and also to estimate ⟨N⟩ from expansion conditions.

Third-generation synchrotrons and high-resolution electron spectrometers coupled with modern theoretical techniques for molecular structure calculations have opened opportunities for measuring carbon 1s ionization energies in a large variety of complex molecules. Recent studies have provided new insights into the chemistry of substituent effects and on the effect of molecular conformation on inner-shell ionization energies.

Carbon 1s photoelectron spectra were measured for 1,1-dichloroethene and 1,3-cyclohexadiene adsorbed on Si(111)-7×7 and for gaseous cyclopentene and 1,1-dichloroethene. We explore closely how the molecular spectra of 1,1-dichloroethene and 1,3-cyclohexadiene change upon physisorption and show how gas-phase X-ray photoelectron spectra can be a useful tool for interpretation of spectra of physisorbed molecules. When assigning spectra of adsorbed states, it is frequently assumed that carbon 1s ionization energies (IE) group according to the hybridization state of the carbon atom and, moreover, that sp3-hybridized carbons have lower ionization energies than do sp2-hybridized carbons. These assumptions are explored by reviewing gas-phase spectra where it is possible to assign spectral peaks to individual carbon atoms without ambiguity. In cyclopentene, the carbon 1s ionization energies do group according to hybridization, albeit with the sp3 carbons at higher IE than the sp2 carbons. In propene, the 1s ionizat...

In N2O a detailed study of the vibrational distribution of the (X) over tilde state reached after decay of core-to-pi* excitation of N terminal, N central and 0 1s core levels is reported. We obser ...

Carbon 1s ionization energies have been measured for all of the carbon atoms in eight fluoromethylbenzenes. Enthalpies of protonation have been calculated for protonation at all of the ring carbons in the same molecules. These data together with previously reported data on fluorobenzenes and methylbenzenes provide the basis for studying the additivity of substituent effects and the correlation between enthalpies of protonation with core-ionization energies. Although a linear additivity model accounts reasonably well for both the ionization energies and the enthalpies of protonation, a better description, especially for the enthalpies, is obtained by inclusion of nonlinear terms that account for interactions between two substituents on the same molecule. There are families of nearly parallel correlation lines between enthalpies of protonation and core-ionization energies. The existence of several families can be primarily understood in terms of the linear additivity picture and more completely understood when the nonlinear terms are taken into account. The role of the methyl group as a polarizible pi-electron donor is contrasted with the role of fluorine, which is a substituent of low polarizibility that acts to withdraw electrons from the adjacent carbon and to donate electrons through resonance to the ring. The role of the hydrogen atoms as pi-electron acceptors in the protonated species is illustrated.

The carbon 1s photoelectron spectrum of 1-pentyne has been recorded with resolution high enough that contributions from inequivalent carbon atoms can be determined. The spectrum is not well described by theoretical lineshape models that are based on either of the anti or the gauche conformations alone. An improved fit is obtained by combining the two single-conformer models, with the composition determined in the fit. This analysis yields 29 ± 3% anti and 71 ± 3% gauche conformers. This result is in agreement with results based on microwave spectroscopy and gas-phase electron diffraction.

Single-component clusters of methyl chloride and methyl bromide have been produced by adiabatic expansion and their C 1s, Cl 2p and Br 3d photoelectron spectra recorded using synchrotron radiation and a high-resolution electron analyzer. The experimentally observed cluster-to-monomer shifts in core-level ionization energies are interpreted in terms of theoretical models based on molecular dynamics (MD) in conjunction with polarizable force fields developed and validated in the course of this work. MD simulations have also been used to explore the global and local structure of the clusters, providing evidence for a predominance of anti-parallel, head-to-tail arrangement of neighboring molecules. Whereas the cluster-to-monomer shifts are strongly dominated by polarization effects, the polarization contribution is very similar for ionization of carbon and the halogen, respectively. The difference in cluster shifts between the two ionization sites within the same molecule, C vs. Cl or C vs. Br, is thus determined by permanent electrostatic moments, i.e. the magnitude and direction of the permanent dipole moment and the local alignment of dipoles.

Chemisorption of 1,1-dichloroethene (Cl2C CH2) to a Si(1 1 1)-7 × 7 surface was studied by means of X-ray photoelectron spectroscopy using synchrotron radiation, recording chlorine 2p and carbon 1s spectra. For carbon 1s, spectral assignment of the chemisorbed species is based on quantum chemical calculations of chemical shifts in model compounds. The results confirm the identity of covalently bonded 1-chlorovinyl (–CCl CH2) and vinylidene ( C CH2) adspecies. Upon chemisorption at room temperature it was found that about one-third of the molecules break one C–Cl bond while about two-thirds of the adsorbates break two C–Cl bonds. We do not, however, find evidence for isomerization of C CH2 to di-bonded vinylene (–CH CH–).

Single-component clusters of methanol and methyl chloride have been produced by adiabatic expansion, and their carbon 1s photoelectron spectra were recorded using synchrotron radiation and a high-resolution electron analyzer. The experimental spectra are interpreted by means of theoretical models based on molecular dynamics simulations. The data are used to explore to what extent core-level photoelectron spectra may provide information on the bonding mechanism and the geometric structure of clusters of polar molecules. The results indicate that the cluster-to-monomer shift in ionization energy and also the width of the cluster peak may be used to distinguish between hydrogen bonding and weaker electrostatic interactions. Moreover, the larger width of the cluster peak in methanol clusters as compared to methyl chloride clusters is partly due to the structured surface of methanol clusters. Theoretical modeling greatly facilitates the analysis of core-level photoelectron spectra of molecular clusters.

High-resolution carbon 1s photoelectron spectra have been measured for methyl-substituted benzenes. By using these data together with molecular structure calculations to predict the vibrational profiles expected in the spectra, it has been possible for the first time to assign 1s ionization energies to each of the inequivalent carbon atoms in these molecules. There exist linear correlations between the ionization energies and the energy changes for other chemical processes, such as enthalpies of protonation and activation energies for hydrogen exchange and protodesilylation. There are deviations from these correlations for sites in which hyperconjugation plays a role in the process. These can be understood by recognizing that the core-ionization energies reflect primarily the Hammett parameter sigma whereas the other energies reflect sigma+. The ionization and reaction energies can be summarized compactly with a linear model in which the total effect of the substituents is equal to the sum of the effects of the individual substituents. A slightly better description is obtained with a quadratic model, which allows for interaction between the substituents.

We have performed a density functional theory investigation of hydroformylation of ethylene for monosubstituted rhodium-carbonyl catalysts, HRh(CO)3L, where the modifying ligand, L, is a phosphite (L = P(OMe)3, P(OPh)3, or P(OCH2CF3)3), a phosphine (L = PMe3, PEt3, PiPr3, or PPh3), or a N-heterocyclic carbene (NHC) based on the tetrahydropyrimidine, imidazol, or tetrazol ring, respectively. The study follows the Heck and Breslow mechanism. Excellent correspondence between our calculations and existing experimental information is found, and the present results constitute the first example of a realistic quantum chemical description of the catalytic cycle of hydroformylation using ligand-modified rhodium carbonyl catalysts. This description explains the mechanistic and kinetic basis of the contemporary understanding of this class of reaction and offers unprecedented insight into the electronic and steric factors governing catalytic activity. The insight has been turned into structure-activity relationships and used as guidelines when also subjecting to calculation phosphite and NHC complexes that have yet to be reported experimentally. The latter calculations illustrate that it is possible to increase the electron-withdrawing capacity of both phosphite and NHC ligands compared to contemporary ligands through directed substitution. Rhodium complexes of such very electron-withdrawing ligands are predicted to be more active than contemporary catalysts for hydroformylation.

Experimental evidence for an effect of molecular conformation on inner-shell ionization energies has been observed for the first time. Examples are seen in the carbon 1s spectra of butyronitrile, 1-fluoropropane, and propanal, and other similar molecules. At room temperature these exist in two different conformations, with different distances and, hence, different Coulombic interactions between the negatively charged electronegative group and the methyl carbon. The experimental results are in accord with theoretical predictions with respect to both ionization energies and populations of the different conformers.

Carbon 1s photoelectron asymmetry parameters beta for the chlorinated and the methyl carbon atom of CH3CH2Cl, CH3CHCl2, and CH3CCl3 have been measured using synchrotron radiation in the 340-600 eV energy range. We provide experimental evidence that the intramolecular scattering strongly affects beta values, even far from the ionization threshold. The results are in agreement with B-spline density functional theory calculations, making it possible to single out the behavior of the various continuum partial waves. We conclude that the intramolecular scattering makes electron angular distributions sensitive to the chemical environment, even in isolated gas phase molecules.

Core-level photoelectron spectra of free neutral methane clusters have been recorded. These spectra exhibit well-resolved surface and bulk features as well as vibrational fine structure. The vibrational structure in the cluster signal is well reproduced by a theoretical model that assumes independent contributions from inter- and intramolecular modes. The intramolecular contribution to the vibrational line-shape is taken to be equal to that of the monomer in the gas phase, while the intermolecular part is simplified to line broadening. An estimate of the cluster size has been made on the basis of the observed surface-to-bulk intensity ratio.

Theoretical models of lineshapes in Ar2p photoionization spectra have been calculated for free, neutral argon clusters of different sizes. The lineshape models are fitted to experimental spectra and used to estimate the mean cluster size realized in the experiment. The results indicate that size estimators working from stagnation conditions [R. Karnbach, M. Joppien, J. Stapelfeldt, J. Wörmer and T.Möller, Rev. Sci. Instrum., 1993, 64, 2838] may underestimate the mean cluster size.

Models of Cr(III)-silica were used to study C-H activation in ethane by oxidative addition as a possible route to catalytic dehydrogenation. This mechanism involves a formal double oxidation of chromium and a minimum energy crossing point (MECP) was located on the seam between the quartet spin potential energy surface of Cr(III) and the doublet spin potential energy surface of Cr(V). Subsequent to the change of spin state, the C-H activation path passes through a transition state on the doublet potential surface, leading to the formation of an ethylhydridochromium(V) complex. This complex represents only a shallow minimum on the potential energy surface and β-hydrogen transfer to complete the catalytic cycle must therefore take place in the extension of the C-H activation step. The combination of a significant activation energy and a small pre-exponential factor in the rate constant makes C-H activation by oxidative addition an unlikely mechanism for dehydrogenation in this system.

Carbon 1s ionization energies have been measured for 12 halomethanes. These together with earlier measurements provide 27 compounds for investigating the relationship between core-ionization energies and the electronegativity and hardness of the halogens. The ionization energies correlate nearly linearly with the sum of the electronegativities of the halogens attached to the central carbon. Both electronegativity and hardness play important roles in determining the ionization energy, and it is found that the linear relationship between ionization energy and electronegativity arises from an interplay of the electronegativity and hardness of the halogens and the length and ionicity of the carbon−halogen bond.

The carbon 1s photoelectron spectra of cyclohexane, cyclohexene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene have been measured. These have been analyzed in terms of a theoretical model of the vibronic structure that includes the effects of the changes in equilibrium geometry that accompany core ionization as well as those of vibronic coupling in the core-ionized molecule. This theoretical approach gives an excellent description of the vibronic structure and makes it possible to identify the contributions of the inequivalent carbon atoms to the spectra. The carbon 1s ionization energies are reported and used in the analysis of photoelectron spectra of adsorbed molecules.

The variation of conductivity with concentration of some onium salts in benzotrifluoride, (1′, 1″, 1″'-trifluoromethylbenzene), BTF, has been studied in the 10−6−10−2 M concentration range. All salts studied display a distinct maximum in the Λ− c 1 2 plots around 1 × 10−5 M preventing Λ° and the degree of dissociation to be determined. The concentration at which Λmax is observed decreases with increasing size of the tetraalkylammonium cations, with decreasing coordinating ability of the anions and with increasing temperature; i.e. with decreasing association constants as deduced from conductivity studies in other solvents. It is suggested that the solvent molecules form pairs or larger aggregates inducing a unique type of solvent-structure-enforced ion-pairing which at very low concentrations will subdue the anticipated increase in the molar conductivity upon further dilution. The presence of head-to-tail anti-parallel dimers in BTF, linked together by F…H interactions, has also been arrived at from quantum chemical calculations. The crystal structure of BTF is not yet known but the crystal structures of some higher-melting compounds like 4-(trifluoromethyl)benzonitrile and 4-(trifluoromethyl)phenylacetonitrile have revealed the presence of weak intermolecular contacts between the fluorine atoms and the aromatic hydrogen atoms but no ππ interactions.

Formation and growth of neutral SO2 clusters is investigated in an adiabatic-expansion setup by means of sulfur 2p (S2p) photoelectron spectroscopy and theoretical modeling. The shift in S2p ionization energy between the cluster and a single molecule, i.e., IE(cluster)-IE(monomer), is recorded and used to monitor the mean cluster size over a wide range of expansion conditions. The produced clusters were shown to fall into two different size regimes. Comparison between theoretical simulations and experimental observations suggests that while the smallest clusters belong to the ultrafine particle mode and have a liquid-like structure, the larger clusters belong to the accumulation mode of fine particles and possibly have a frozen cluster core. The transition between the two size/structure regimes occurs over a narrow interval in expansion conditions and may possibly reflect a change in growth mechanism from monomer addition to growth by cluster-cluster collisions.(c) Jarle Harnes, Mahmoud Abu-Samha, Mathias Winkler, and Knut J. Børve

Carbon 1s photoelectron spectra for CF4 and CO have been measured at several photon energies near the carbon 1s threshold. The spectra have been analyzed in terms of the vibrational structure and the natural linewidth. For CO the vibrational structure shows evidence for anharmonicity in both the energy spacing and the intensity. Analysis of the results using an anharmonic model gives an equilibrium bond length for core-ionized CO that is 4.85 pm shorter than that of neutral CO. For CF4, the vibrational structure is very weak, and the analysis shows that the change in equilibrium CF bond length upon ionization is no more than 0.54 pm. Ab initio theoretical calculations give results in accord with these bond-length changes. The unusually small bond-length contraction in CF4 can be understood in terms of nonbonded fluorine–fluorine repulsion. The natural linewidth for core-ionized CO, 95±5 meV, is essentially the same as that of CH4. This result is in contrast with expectations based on the one-center model ...

Vibrational structures of the C1s and N1s photoelectron spectra of gas-phase HCN have been investigated using monochromated third-generation synchrotron radiation. Both spectra exhibit resolved fine structure associated with several vibrationally excited states. In the C1s spectrum a single vibrational progression is observed, while the N1s spectrum is more complex. High-level ab initio calculations were performed to simulate the spectra and the agreement with the experimental results is good. Based on the calculations, the C1s ionisation is found to induce vibrations solely in the CN stretching mode with an energy of 280 meV, while the N1s ionisation generates vibrations also in the CH stretching mode with an energy of about 387 meV, as well as combinations of these two modes.

Prospects of ethylene polymerization over pseudo-octahedral mononuclear Cr(II) sites as well as tetrahedral mononuclear Cr(II)-B sites with a coordinating silanol moiety have been examined by means of cluster models and gradient-corrected density functional theory. For the octahedral site, candidate active sites are considered to arise through reactions between ethylene and chromium. In the case of a Cr(II)-B site, the added complexity of reactive interactions with the coordinating silanol moiety is taken into account. In the case of propagation, emphasis is put on monomer insertion into a chromium–carbon single bond in four-coordinated Cr(IV) species. The mononuclear Cr(II)-B site is found to afford activation through hydrogen transfer from the coordinating silanol group, given that the silica matrix offers a minimum of strain to prepare the structure for ethylene coordination.

Vibrationally resolved C1s photoelectron spectra of benzene and d6-benzene have been recorded using monochromated synchrotron radiation at photon energies of 330 eV. The spectrum of normal benzene displays considerable vibrational structure. Particularly noteworthy is the strong excitation of a combined CCH-bending and CC-stretching mode which splits the main peak into two well-defined maxima. In d6-benzene, the vibrational energy levels are less well separated and the vibrational structure is reduced to strong asymmetry of the main peak and a broad tail extending toward higher ionization energy. The recorded spectra are analyzed using first-principle and curve-fitting procedures. A theoretical model that allows for incomplete localization of the core hole, results in very good fits to the experimental spectra of both benzene and d6-benzene.

Cluster models are constructed for mononuclear Cr(II) and Cr(III) sites as well as dinuclear Cr(II) sites of the reduced Cr/SiO2-based Phillips catalyst. The binding energies and structures of oligocarbonyl complexes formed at these cluster models have been computed using density functional theory. Furthermore, harmonic frequencies and infrared intensities are calculated for the carbonyl stretching modes of these complexes. The resulting parameters are compared to literature spectra of CO-exposed Phillips catalysts and related model systems. A reassignment is proposed for the infrared spectrum of carbon monoxide on the reduced Cr/silica system.

Adiabatic expansion of molecular vapors is a celebrated method for producing pure and mixed clusters of relevance in both applied and fundamental studies. The present understanding of the relationship between experimental conditions and the structure of the clusters formed is incomplete. We explore the role of the backing/carrier gas during adiabatic expansion of ethanol vapors with regard to cluster production and composition. Single-component clusters of ethanol were produced over a wide size-range by varying the rare gas (He, Ar) backing pressure, with Ar being more efficient than He in promoting the formation of pure ethanol clusters. However, at stagnation pressures Ps>1.34(4) bar and temperature 49(2) °C, synchrotron-based valence and inner-shell photoelectron spectroscopy reveals condensation of Ar carrier gas on the clusters. Theoretical calculations of cluster geometries as well as chemical shifts in carbon 1s ionization energies confirm that the experimental observations are consistent with an ethanol core covered by an outer shell of argon. Experiments on the 1-propanol/Ar system display a similar pattern as described for ethanol/Ar, indicating a broader range of validity of the results.

The electron effective attenuation length (EAL) in free, neutral ethane clusters has been determined at 40 eV kinetic energy by combining carbon 1s x-ray photoelectron spectroscopy and theoretical lineshape modeling. More specifically, theory is employed to form model spectra on a grid in cluster size (N) and EAL (λ), allowing N and λ to be determined by optimizing the goodness-of-fit χ(2)(N, λ) between model and observed spectra. Experimentally, the clusters were produced in an adiabatic-expansion setup using helium as the driving gas, spanning a range of 100-600 molecules in mean cluster size. The effective attenuation length was determined to be 8.4 ± 1.9 Å, in good agreement with an independent estimate of 10 Å formed on the basis of molecular electron-scattering data and Monte Carlo simulations. The aggregation state of the clusters as well as the cluster temperature and its importance to the derived EAL value are discussed in some depth.

HCl dissociation in methanol clusters is studied by ab initio molecular dynamics simulations and experimentally by X-ray photoelectron spectroscopy. From theoretical simulations of HCl in oligomers and medium-sized clusters of methanol, two states of solvation are identified for HCl: an intermediate proton-sharing (ion pair) state and a fully dissociated state. Lowering the temperature from 150 to 100 K is found to promote full dissociation over the proton-sharing state. The dissociation of HCl is well reflected in the experimental chlorine 2p photoelectron spectrum recorded for a beam of clusters formed by adiabatic expansion of the vapor over a solution of HCl in methanol. In order to reproduce the observed Cl 2p spectrum by means of theoretical line-shape modeling, one needs to take into account both the intermediate proton-sharing state and the fully dissociated state.

High-resolution molecular X-ray photoelectron spectra of second-row atoms may reveal broadening or even splitting of the 2p 3/2 peak as compared to the 2p 1/2 component of the spectrum. This splitting reflects the lifted degeneracy of atomic 2p orbitals at sites of less than cubic symmetry and is referred to as molecular-field splitting (MFS). The prospect of using second-order Moller–Plesset theory (MP2) for ab initio calculation of the MFS for sulfur 2p 3/2 levels is examined. This method is subsequently applied to compute the MFS in ethynyl, ethenyl, and ethyl sulfur pentafluoride, resulting in values of 80, 116 and 121 meV, respectively. The initial-state contribution to the splitting is analyzed in terms of asymmetry in the electron density at sulfur, on the one hand, and in terms of the sulfur-ligand overlap density and electron density at the groups bonded to sulfur, on the other. At the Koopmans' theorem level of theory, the main source of splitting in the title compounds is found to be s–d hybridization of sulfur. At post-SCF levels of theory, core-valence electron correlation contributes substantially to the MFS, in proportion to the occupational asymmetry of the S3p shell. The realization that mixing of sulfur atomic orbitals of the same parity may add important contributions to the electric-field gradient at the core, resolves the observed diversity in the relative importance of core-valence electron correlation between different classes of sulfur compounds.

Direct insertion of ethylene into the chromium−carbon bond in singly charged bis(imido)chromium(VI) cations has been investigated for n-alkyl and benzyl as starting polymer chains. Frontside coordination of ethylene takes place without activation to give a stable complex. Subsequent insertion into the Cr−alkyl bond requires a free energy of activation of 15 kcal/mol and an even higher barrier in the case of a benzyl ligand. Near the transition state, the reaction coordinate is dominated by inversion of the metal complex. Ethylene coordination in the backside mode requires considerable activation, and the additional increase in free energy through loss of entropy makes direct coordination unlikely. An indirect route to the β-agostic backside π-complex is found by inversion of the corresponding frontside ethylene−chromium complex. This rearrangement takes place via a transition state that has comparable or slightly lower free energy than that of direct insertion starting from the frontside π-complex. Howeve...