Energy-Dependent Relative Cross Sections in Carbon 1s Photoionization: Separation of Direct Shake and Inelastic Scattering Effects in Single Molecules.

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.

Attenuation of slow (10-40 eV) electrons in soft nanoparticles: Size matters in argon clusters.

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.

Changing role of carrier gas in formation of ethanol clusters by adiabatic expansion.

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.

Electronic Properties of Chlorine, Methyl, and Chloromethyl as Substituents to the Ethylene Group--Viewed from the Core of Carbon.

"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 sp(2) carbon (ß 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.

HCl dissociation in methanol clusters from ab initio molecular dynamics simulations and inner-shell photoelectron spectroscopy.

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.

Intensity oscillations in the carbon 1s ionization cross sections of 2-butyne.

Carbon 1s photoelectron spectra for 2-butyne (CH3C≡CCH3) measured in the photon energy range from threshold to 150 eV above threshold show oscillations in the intensity ratio C2,3/C1,4. Similar oscillations have been seen in chloroethanes, where the effect has been attributed to EXAFS-type scattering from the substituent chlorine atoms. In 2-butyne, however, there is no high-Z atom to provide a scattering center and, hence, oscillations of the magnitude observed are surprising. The results have been analyzed in terms of two different theoretical models: a density-functional model with B-spline atom-centered functions to represent the continuum electrons and a multiple-scattering model using muffin-tin potentials to represent the scattering centers. Both methods give a reasonable description of the energy dependence of the intensity ratios.

Conformations and CH/π interactions in aliphatic alkynes and alkenes.

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.

Chemical reactivity of alkenes and alkynes as seen from activation energies, enthalpies of protonation, and carbon 1s ionization energies.

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.

On the origins of core-electron chemical shifts of small biomolecules in aqueous solution: insights from photoemission and ab initio calculations of glycine(aq).

The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon 1s binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.

Accuracy of Calculated Chemical Shifts in Carbon 1s Ionization Energies from Single-Reference ab Initio Methods and Density Functional Theory.

A database of 77 adiabatic carbon 1s ionization energies has been prepared, covering linear and cyclic alkanes and alkenes, linear alkynes, and methyl- or fluoro-substituted benzenes. Individual entries are believed to carry uncertainties of less than 30 meV in ionization energies and less than 20 meV for shifts in ionization energies. The database provides an unprecedented opportunity for assessing the accuracy of theoretical schemes for computing inner-shell ionization energies and their corresponding chemical shifts. Chemical shifts in carbon 1s ionization energies have been computed for all molecules in the database using Hartree-Fock, Møller-Plesset (MP) many-body perturbation theory of order 2 and 3 as well as various approximations to full MP4, and the coupled-cluster approximation with single- and double-excitation operators (CCSD) and also including a perturbational estimate of the energy effect of triple-excitation operators (CCSD(T)). Moreover, a wide range of contemporary density functional theory (DFT) methods are also evaluated with respect to computing experimental shifts in C1s ionization energies. Whereas the top ab initio methods reproduce the observed shifts almost to within the experimental uncertainty, even the best-performing DFT approaches meet with twice the root-mean-squared error and thrice the maximum error compared to CCSD(T). However, a number of different density energy functionals still afford sufficient accuracy to become tools in the analysis of complex C1s photoelectron spectra.

Additivity of substituent effects. Core-ionization energies and substituent effects in fluoromethylbenzenes.

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 substituent effect of the methyl group. Carbon 1s ionization energies, proton affinities, and reactivities of the methylbenzenes.

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.

Activity of rhodium-catalyzed hydroformylation: added insight and predictions from theory.

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.

Structure and stability of networked metallofullerenes of the transition metals.

A DFT investigation of substitutionally doped fullerenes MC59 of second- and third-row transition metals shows that their stability increases toward the right-hand side of the d-block. Whereas the structural deviation from that of C60 depends on the size of the metal atom, stability is governed by electronic properties of the transition metal atom. A range of MC59 compounds of group 6-8 metals are predicted to have sufficient stability for experimental observation.

Fluorine as a pi donor. Carbon 1s photoelectron spectroscopy and proton affinities of fluorobenzenes.

The carbon 1s ionization energies for all of the carbon atoms in 10 fluorine-substituted benzene molecules have been measured by high-resolution photoelectron spectroscopy. A total of 30 ionization energies can be accurately described by an additivity model with four parameters that describe the effect of a fluorine that is ipso, ortho, meta, or para to the site of ionization. A similar additivity relationship describes the enthalpies of protonation. The additivity parameters reflect the role of fluorine as an electron-withdrawing group and as a pi-electron donating group. The ionization energies and proton affinities correlate linearly, but there are four different correlations depending on whether there are 0, 1, 2, or 3 fluorines ortho or para to the site of ionization or protonation. That there are four correlation lines can be understood in terms of the ability of the hydrogens at the site of protonation to act as a pi-electron acceptor. A comparison of the ionization energies and proton affinities, together with the results of electronic structure calculations, gives insight into the effects of fluorine as an electron-withdrawing group and as a pi donor, both in the neutral molecule and in response to an added positive charge.

Reactivity and core-ionization energies in conjugated dienes. Carbon 1s photoelectron spectroscopy of 1,3-pentadiene.

The high-resolution carbon 1s photoelectron spectrum of trans-1,3-pentadiene has been resolved into contributions from the five inequivalent carbon atoms, and carbon 1s ionization energies have been assigned to each of these atoms. Spectra have also been measured for propene and 1,3-butadiene at better resolution than has previously been available. The ionization energies for the sp2 carbons are found to correlate well with activation energies for electrophilic addition and with proton affinities. Comparing the results for 1,3-pentadiene with those for ethene, propene, and 1,3-butadiene as well as with results of theoretical calculations makes it is possible to assess the effect of the terminal methyl group in 1,3-pentadiene. As in propene, the methyl group contributes electrons to the beta carbon through the pi system. In addition, there is a significant (though smaller) contribution from the methyl group to the terminal (delta) CH2 carbon, also through the pi system. Most of the effect of the methyl group is present in the ground-state molecule. There are only relatively small contributions from the methyl group to the ionization energies from redistribution of charge in the pi system in response to the removal of a core electron. In addition to these specific effects, there is an overall decrease in average ionization energy as the size of the molecule increases as well as effects that are specific to the conjugated systems in 1,3-butadiene and 1,3-pentadiene. The results provide insight into the reactivity and regioselectivity of conjugated dienes.

Reduction of chromium in ethylene polymerisation using bis(imido)chromium(VI) catalyst precursors.

Hybrid density functional calculations on [Cr(NR)2C3H7(C2H4)]+ (R = H, tBu) have revealed a facile reductive elimination reaction involving beta-hydrogen transfer from the alkyl chain, suggesting that the active species in ethylene polymerisation with bis(imido)chromium(VI) precursors contains a reduced chromium atom.

Toward the spectrum of free polyethylene: linear alkanes studied by carbon 1s photoelectron spectroscopy and theory.

Trends in carbon 1s ionization energies for the linear alkanes have been investigated using third-generation synchrotron radiation. The study comprises CH(4), C(2)H(6), C(3)H(8), C(4)H(10), C(5)H(12), C(6)H(14), and C(8)H(18). Both inter- and intramolecular shifts in ionization energy have been determined from gas-phase spectra and ab initio calculations. The shifts are decomposed into initial-state and final-state contributions and are shown to relate to the fundamental chemical properties of group electronegativity and polarizability. By extrapolation, we predict C1s spectra of larger n-alkanes, converging toward isolated strands of polyethylene.