Abrupt Change from Ionic to Covalent Bonding in Nickel Halides Accompanied by Ligand Field Inversion.

The electronic configuration of transition metal centers and their ligands is crucial for redox reactions in metal catalysis and electrochemistry. We characterize the electronic structure of gas-phase nickel monohalide cations via nickel L2,3-edge X-ray absorption spectroscopy. Comparison with multiplet charge-transfer simulations and experimental spectra of selectively prepared nickel monocations in both ground- and excited-state configurations are used to facilitate our analysis. Only for [NiF]+ with an assigned ground state of 3Π can the bonding be described as predominantly ionic, while the heavier halides with assigned ground states of 3Π or 3Δ exhibit a predominantly covalent contribution. The increase in covalency is accompanied by a transition from a classical ligand field for [NiF]+ to an inverted ligand field for [NiCl]+, [NiBr]+, and [NiI]+, resulting in a leading 3d9 L̲ configuration with a ligand hole (L̲) and a 3d occupation indicative of nickel(I) compounds. Hence, the absence of a ligand hole in [NiF]+ precludes any ligand-based redox reactions. Additionally, we demonstrate that the shift in energy of the L3 resonance is reduced compared to that of isolated atoms upon the formation of covalent compounds.

Soft X-ray absorption and fragmentation of tin-oxo cage photoresists.

"Tin-oxo cage" organometallic compounds are considered as photoresists for extreme ultraviolet (EUV) photolithography. To gain insight into their electronic structure and reactivity to ionizing radiation, we trapped bare gas-phase n-butyltin-oxo cage dications [(BuSn)12O14(OH)6]2+ in an ion trap and investigated their fragmentation upon soft X-ray photoabsorption by means of mass spectrometry. In complementary experiments, the tin-oxo cages with hydroxide and trifluoroacetate counter-anions were cast in thin films and studied using X-ray transmission spectroscopy. Quantum-chemical calculations were used to interpret the observed spectra. At the carbon K-edge, a distinct pre-edge absorption band can be attributed to transitions in which electrons are promoted from C1s orbitals to the lowest unoccupied molecular orbitals, which are delocalized orbitals with strong antibonding (Sn-C σ*) character. At higher energies, the most prominent resonant transitions involve C-C and C-H σ* valence states and Rydberg (3s and 3p) states. In the solid state, the onset of continuum ionization is shifted by ∼5 eV to lower energy with respect to the gas phase, due to the electrostatic effect of the counterions. The O K-edge also shows a pre-edge absorption, but it is devoid of any specific features, because there are many transitions from the different O1s orbitals to a large number of vacant orbitals. In the gas phase, formation of the parent [(BuSn)12O14(OH)6]3+ radical ion is not observed at the C K-edge nor at the O K-edge, because the loss of a butyl group from this species is very efficient. We do observe a number of triply charged photofragment ions, some of which have lost up to 5 butyl groups. Structures of these species are proposed based on quantum-chemical calculations, and pathways of formation are discussed. Our results provide insight into the electronic structure of alkyltin-oxo cages, which is a prerequisite for understanding their response to EUV photons and their performance as EUV photoresists.

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4 ].

The tetraoxido ruthenium(VIII) radical cation, [RuO4 ]+ , should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO4 ]+ , produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO4 ]+ is identified by the chemical shift at the ruthenium M3 edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO4 ]+ to the closed-shell [RuO4 H]+ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO4 ]+ than for [OsO4 ]+ .

Mn12 -Acetate Complexes Studied as Single Molecules.

The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn12 coordination clusters of general formula [MnIII 8 MnIV 4 O12 (RCOO)16 (H2 O)4 ] had been exemplified by bulk samples of the archetypal [MnIII 8 MnIV 4 O12 (CH3 COO)16 (H2 O)4 ] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn12 system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn12 O12 (CH3 COO)15 (CH3 CN)]+ (1) by gas phase X-ray Magnetic Circular Dichroism (XMCD) spectroscopy, and we find it closely resembling that of the corresponding bulk samples. Furthermore, we report broken symmetry DFT calculations of spin densities and single ion tensors of the isolated, optimized complexes [Mn12 O12 (CH3 COO)15 (CH3 CN)]+ (1), [Mn12 O12 (CH3 COO)16 ] (2), [Mn12 O12 (CH3 COO)16 (H2 O)4 ] (3), and the complex in bulk geometry [MnIII 8 MnIV 4 O12 (CH3 COO)16 (H2 O)4 ] (5). The found magnetic fingerprints - experiment and theory alike - are of a remarkable robustness: The MnIV 4 core bears almost no magnetic anisotropy while the surrounding MnIII 8 ring is highly anisotropic. These signatures are truly intrinsic properties of the Mn12 core scaffold within all of these complexes and largely void of the environment. This likely holds irrespective of bulk packing effects.

Anion photoelectron spectroscopy and density functional theory study of TM2Sin- (TM = V, Cr; n = 14-20) clusters.

We investigated the structural evolution and electronic properties of medium-sized silicon cluster anions doped with two transition metal atoms, TM2Sin- (TM = V, Cr; n = 14-20), by using mass-selective anion photoelectron spectroscopy combined with density functional theory (DFT) calculations. Putative ground state structures of these clusters were obtained by using a genetic algorithm coupled with the DFT calculations. It was found that the two TM atoms tend to form a TM-TM bond, which - except for V2Si19- - is shorter than the nearest neighbour distance in the crystalline state of the respective metals. The V2Sin- clusters with n = 14 to 17 exhibit structures based on a silicon hexagonal antiprism, while the larger ones exhibit more fullerene-like cage structures. Cr2Sin- clusters follow the same trend, although with a silicon hexagonal prism structure for n = 14 and 15, and the transition to fullerene-like structures occurring at n = 17. Among these clusters, TM2Si18- have the largest average binding energy and second order differences in energy, therefore the highest relative stability. All of the clusters possess total magnetic moment of 1 µB, but with very different contributions from the doped TM atoms. Especially in the Cr doped clusters there is a tendency towards an anitiferromagnetic arrangement of the magnetic moments of the two Cr atoms.

Structures and electronic properties of VSin- (n = 14-20) clusters: a combined experimental and density functional theory study.

We present a systematic study of the structures and electronic properties of vanadium-doped silicon cluster anions, VSin- (n = 14-20), by combining photoelectron spectroscopy (PES) measurements and density functional theory (DFT) based theoretical calculations. High resolution PES of low temperature (10 K) clusters are acquired at a photon wavelength of 248 nm. Low-lying structures of VSi14-20- are obtained by a genetic algorithm based global minimum search code combined with DFT calculations. Excellent agreement is found between the measured PES and the simulated electron density of states of the putative ground-state structures. We conclude that clusters with sizes n = 14 and n = 15 prefer cage-like structures, with the encapsulated vanadium atom bonding with all silicon atoms, while a fullerene-like motif is more favorable for n ≥ 16. For the sizes n = 16 to 19, the structures consist of a V@Si14 with two, three, four, and five Si atoms on the surface of the cage. For n = 20 the structure consists of a V@Si15 with five Si atoms on the surface of the cage. VSi14- has the highest stability and stands out as a simultaneous closing of electronic and geometrical shells.

Soft X-ray signatures of cationic manganese-oxo systems, including a high-spin manganese(V) complex.

Manganese-oxo species catalyze key reactions, including C-H bond activation or dioxygen formation in natural photosynthesis. To better understand relevant reaction intermediates, we characterize electronic states and geometric structures of [MnOn]+ manganese-oxo complexes that represent a wide range of manganese oxidation states. To this end, we apply soft X-ray spectroscopy in a cryogenic ion trap, combined with multiconfigurational wavefunction calculations. We identify [MnO2]+ as a rare high-spin manganese(V) oxo complex with key similarities to six-coordinated manganese(V) oxo systems that are proposed as reaction intermediates in catalytic dioxygen bond formation.

Iron L3-edge energy shifts for the full range of possible 3d occupations within the same oxidation state of iron halides.

Oxidation states are integer in number but dn configurations of transition metal centers vary continuously in polar bonds. We quantify the shifts of the iron L3 excitation energy, within the same formal oxidation state, in a systematic L-edge X-ray absorption spectroscopy study of diatomic gas-phase iron(II) halide cations, [FeX]+,where X = F, Cl, Br, I. These shifts correlate with the electronegativity of the halogen, and are attributed exclusively to a fractional increase in population of 3d-derived orbitals along the series as supported by charge transfer multiplet simulations and density functional theory calculations. We extract an excitation energy shift of 420 meV ± 60 meV spanning the full range of possible 3d occupations between the most ionic bond in [FeF]+ and covalently bonded [FeI]+.

Intramolecular hydrogen transfer in DNA induced by site-selective resonant core excitation.

We present experimental evidence for soft X-ray induced intramolecular hydrogen transfer in the protonated synthetic tri-oligonucleotide d(FUAG) in the gas-phase (FU: fluorouracil). The trinucleotide cations were stored in a cryogenic ion trap and exposed to monochromatic synchrotron radiation. Photoionization and photofragmentation product ion yields were recorded as a function of photon energy. Predominanly glycosidic bond cleavage leading to formation of nucleobase-related fragments is observed. In most cases, glycosidic bond cleavage is accompanied by single or double hydrogen transfer. The combination of absorption-site-sensitive soft X-ray spectroscopy with fragment specific mass spectrometry allows to directly relate X-ray absorption site and fragmentation site. We observe pronounced resonant features in the competition between single and double hydrogen transfer towards nucleobases. A direct comparison of experimental data with time-dependent density functional theory calculations, using short range corrected hybrid functionals, reveal that these hydrogen transfer processes are universal and not limited to population of particular excited states localized at the nucleobases. Instead, hydrogen transfer can occur upon X-ray absorption in any nucleobase and in the DNA backbone. Resonances seem to occur because of site-selective suppression of hydrogen transfer channels. Furthermore, non-covalent interactions of the optimized ground state geometries were investigated to identify intramolecular hydrogen bonds along which hydrogen transfer is most likely.

Photoelectron Spectroscopy and Density Functional Investigation of the Structural Evolution, Electronic, and Magnetic Properties of CrSin- (n = 14-18) Clusters.

CrSin- (n = 14-18) cluster anions have been investigated by a combination of photoelectron spectroscopy (PES) and first-principles calculations. The lowest-lying structures of the clusters have been determined by a global minimum search based on the genetic algorithm, combined with density functional theory (DFT) calculations. The simulated PES spectra of the lowest-energy isomers are in agreement with the experimental results, which gives strong evidence that the correct structures have been found. While sizes n = 14 and n = 15 prefer cage-like structures based on multi-center bonding within the cage, the larger sizes adopt structures based on fullerene-type cages around the Cr atom, with the additional atoms attached to the cage surface. A Hirshfeld analysis shows that the Cr atoms act as electron donors in all clusters, thus enhancing the electron count in the cage. It also reveals that the magnetic moment of 1µB shown by all clusters is mainly contributed by the Cr atom. One interesting exception is size 17, where the Cr atom contributes a small moment antiparallel to that of the silicon cage.

X-ray Induced Fragmentation of Protonated Cystine.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur L-edge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

The Highest Oxidation State of Rhodium: Rhodium(VII) in [RhO3 ].

Although the highest possible oxidation states of all transition elements are rare, they are not only of fundamental interest but also relevant as potentially strong oxidizing agents. In general, the highest oxidation states are found in the electron-rich late transition elements of groups 7-9 of the periodic table. Rhodium is the first element of the 4d transition metal series for which the highest known oxidation state does not equal its group number of 9, but reaches only a significantly lower value of +6 in exceptional cases. Higher oxidation states of rhodium have remained elusive so far. In a combined mass spectrometry, X-ray absorption spectroscopy, and quantum-chemical study of gas-phase R h O n + (n=1-4), we identify R h O 3 + as the 1 A 1 ' trioxidorhodium(VII) cation, the first chemical species to contain rhodium in the +7 oxidation state, which is the third-highest oxidation state experimentally verified among all elements in the periodic table.

Decoherence-Induced Universality in Simple Metal Cluster Photoelectron Angular Distributions.

Measured angular distributions of photoelectrons from size-selected copper and sodium cluster anions are demonstrated to exhibit a universal behavior independent of the initial electron state, cluster size, or material, which can be traced back to momentum conservation upon photoemission. Quantum simulations reproduce the universality under the assumption that multielectron dynamics localizes the emission on the cluster surface and renders the cluster opaque to photoelectrons, thereby quenching interference effects that would otherwise obscure this almost classical behavior.

Site-selective soft X-ray absorption as a tool to study protonation and electronic structure of gas-phase DNA.

The conformation and the electronic structure of gas-phase oligonucleotides depends strongly on the protonation site. 5'-d(FUAG) can either be protonated at the A-N1 or at the G-N7 position. We have stored protonated 5'-d(FUAG) cations in a cryogenic ion trap held at about 20 K. To identify the protonation site and the corresponding electronic structure, we have employed soft X-ray absorption spectroscopy at the nitrogen K-edge. The obtained spectra were interpreted by comparison to time-dependent density functional theory calculations using a short-range exchange correlation functional. Despite the fact that guanine has a significantly higher proton affinity than adenine, the agreement between experiment and theory is better for the A-N1 protonated system. Furthermore, an inverse site sensitivity is observed in which the yield of the nucleobase fragments that contain the absorption site appears substantially reduced, which could be explained by non-statistical fragmentation processes, localized on the photoabsorbing nucleobase.

Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N2H.

As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab initio calculations we show that the spectrum consists of a superposition of two nitrogen 1s absorption spectra, each including a π* band, and a nitrogen 1s to H+ charge transfer band followed by a weak irregular progression of high energy excitations. Calculations also show that, as an effect of symmetry breaking by protonation, the π* transitions are separated by 0.23 eV, only slightly exceeding the difference in the corresponding dark (symmetry forbidden) and bright (symmetry allowed) core excitations of neutral N2. By DFT and calculations and vibrational analysis, the complex π* excitation band of N2H+ is understood as due to the superposition of the significantly different vibrational progressions of excitations from terminal and central nitrogen atoms, both leading to bent final state geometries. We also show computationally that the electronic structure of the charge transfer excitation smoothly depends on the nitrogen-proton distance and that there is a clear extension of the spectra going from infinity to close nitrogen-proton distance where fine structures show some, although not fully detailed, similarities. An interesting feature of partial localization of the nitrogen core orbitals, with a strong, non-monotonous, variation with nitrogen-proton distance could be highlighted. Specific effects could be unraveled when comparing molecular cation NEXAFS spectra, as represented by recently recorded spectra of N2+ and CO+, and spectra of protonated molecules as represented here by the N2H+ ion. Both types containing rich physical effects not represented in NEXAFS of neutral molecules because of the positive charge, whereas protonation also breaks the symmetry. The effect of the protonation on dinitrogen can be separated in charge, which extends the high-energy part of the spectrum, and symmetry-breaking, which is most clearly seen in the low-energy π* transition.

Photoelectron Spectroscopy of Large Water Cluster Anions.

Photoelectron spectra of large size selected water cluster anions (H2O)n- (n = 100-1100) have been measured at a low cluster temperature (80 K). An extensive peak analysis has been conducted in order to determine average and isomer-resolved vertical detachment energies (VDE) of the hydrated electron. This allows us, in combination with the reevaluated data of the previously reported results on small- and medium-sized water cluster anions ( J. Chem. Phys. 2009, 131, 144303), to draw a comprehensive picture of the size-dependent development of the VDEs of water clusters. This allows for an improved extrapolation of the cluster VDEs to the bulk, which yields a value of 3.60 ± 0.03 eV. The general size dependence of the VDEs is in very good agreement with a standard dielectric model.

The carbon and oxygen K-edge NEXAFS spectra of CO.

We present and analyze high resolution near edge X-ray absorption fine structure (NEXAFS) spectra of CO+ at the carbon and oxygen K-edges. The spectra show a wealth of features that appear very differently at the two K-edges. The analysis of these features can be divided into three parts; (i) repopulation transition to the open shell orbital - here the C(1s) or O(1s) to 5σ transition, where the normal core hole state is reached from a different initial state and different interaction than in X-ray photoelectron spectroscopy; (ii) spin coupled split valence bands corresponding to C(1s) or O(1s) to π* transitions; (iii) remainder weak and long progressions towards the double ionization potentials containing a manifold of peaks. These parts, none of which has correspondence in NEXAFS spectra of neutral molecules, are dictated by the localization of the singly occupied 5σ orbital, adding a dimension of chemistry to the ionic NEXAFS technique.

Experimental and theoretical 2p core-level spectra of size-selected gas-phase aluminum and silicon cluster cations: chemical shifts, geometric structure, and coordination-dependent screening.

We present 2p core-level spectra of size-selected aluminum and silicon cluster cations from soft X-ray photoionization efficiency curves and density functional theory. The experimental and theoretical results are in very good quantitative agreement and allow for geometric structure determination. New ground state geometries for Al12+, Si15+, Si16+, and Si19+ are proposed on this basis. The chemical shifts of the 2p electron binding energies reveal a substantial difference for aluminum and silicon clusters: while in aluminum the 2p electron binding energy decreases with increasing coordination number, no such correlation was observed for silicon. The 2p binding energy shifts in clusters of both elements differ strongly from those of the corresponding bulk matter. For aluminum clusters, the core-level shifts between outer shell atoms and the encapsulated atom are of opposite sign and one order of magnitude larger than the corresponding core-level shift between surface and bulk atoms in the solid. For silicon clusters, the core-level shifts are of the same order of magnitude in clusters and in bulk silicon but no obvious correlation of chemical shift and bond length, as present for reconstructed silicon surfaces, are observed.

Soft X-ray Spectroscopy as a Probe for Gas-Phase Protein Structure: Electron Impact Ionization from Within.

Preservation of protein conformation upon transfer into the gas phase is key for structure determination of free single molecules, for example using X-ray free-electron lasers. In the gas phase, the helicity of melittin decreases strongly as the protein's protonation state increases. We demonstrate the sensitivity of soft X-ray spectroscopy to the gas-phase structure of melittin cations ([melittin+qH]q+ , q=2-4) in a cryogenic linear radiofrequency ion trap. With increasing helicity, we observe a decrease of the dominating carbon 1 s-π* transition in the amide C=O bonds for non-dissociative single ionization and an increase for non-dissociative double ionization. As the underlying mechanism we identify inelastic electron scattering. Using an independent atom model, we show that the more compact nature of the helical protein conformation substantially increases the probability for off-site intramolecular ionization by inelastic Auger electron scattering.

Access to the Bis-benzene Cobalt(I) Sandwich Cation and its Derivatives: Synthons for a "Naked" Cobalt(I) Source?

The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2 (CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF )4 ]- and [F{Al(ORF )3 }2 ]- {RF =C(CF3 )3 } and the solvent ortho-difluorobenzene (o-DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o-dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low-coordinate 12 valence electron Co(Pt Bu3 )2+ and Co(NHC)2+ salts.