Strong-field quantum control in the extreme ultraviolet domain using pulse shaping.

Tailored light-matter interactions in the strong coupling regime enable the manipulation and control of quantum systems with up to unit efficiency, with applications ranging from quantum information to photochemistry. Although strong light-matter interactions are readily induced at the valence electron level using long-wavelength radiation, comparable phenomena have been only recently observed with short wavelengths, accessing highly excited multi-electron and inner-shell electron states. However, the quantum control of strong-field processes at short wavelengths has not been possible, so far, because of the lack of pulse-shaping technologies in the extreme ultraviolet (XUV) and X-ray domain.

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 L-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.

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 -butyltin-oxo cage dications [(BuSn)O(OH)] 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.

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

The tetraoxido ruthenium(VIII) radical cation, [RuO ] , 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 [RuO ] , 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 [RuO ] is identified by the chemical shift at the ruthenium M 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 [RuO ] to the closed-shell [RuO H] ion.

Three-dimensional femtosecond snapshots of isolated faceted nanostructures.

The structure and dynamics of isolated nanosamples in free flight can be directly visualized via single-shot coherent diffractive imaging using the intense and short pulses of x-ray free-electron lasers. Wide-angle scattering images encode three-dimensional (3D) morphological information of the samples, but its retrieval remains a challenge. Up to now, effective 3D morphology reconstructions from single shots were only achieved via fitting with highly constrained models, requiring a priori knowledge about possible geometries.

Iron L-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 d configurations of transition metal centers vary continuously in polar bonds. We quantify the shifts of the iron L 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.

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

We investigated the structural evolution and electronic properties of medium-sized silicon cluster anions doped with two transition metal atoms, TMSi (TM = V, Cr; = 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 VSi - is shorter than the nearest neighbour distance in the crystalline state of the respective metals.

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

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.

Structures and electronic properties of VSi ( = 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, VSi ( = 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 VSi are obtained by a genetic algorithm based global minimum search code combined with DFT calculations.

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 (UAG) in the gas-phase (U: 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.

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.

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

CrSi ( = 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.

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 [MnO] 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.

Mn -Acetate Complexes Studied as Single Molecules.

The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn coordination clusters of general formula [Mn Mn O (RCOO) (H O) ] had been exemplified by bulk samples of the archetypal [Mn Mn O (CH COO) (H O) ] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn O (CH COO) (CH 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 [Mn O (CH COO) (CH CN)] (1), [Mn O (CH COO) ] (2), [Mn O (CH COO) (H O) ] (3), and the complex in bulk geometry [Mn Mn O (CH COO) (H O) ] (5).

Photoelectron Spectroscopy of Large Water Cluster Anions.

Photoelectron spectra of large size selected water cluster anions (HO) ( = 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 ( 2009, 131, 144303), to draw a comprehensive picture of the size-dependent development of the VDEs of water clusters.

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

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 NH. 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.

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.

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy.

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin.

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.

Probing Structural Information of Gas-Phase Peptides by Near-Edge X-ray Absorption Mass Spectrometry.

Near-edge X-ray absorption mass spectrometry (NEXAMS) is an action-spectroscopy technique of growing interest for investigations into the spatial and electronic structure of biomolecules. It has been used successfully to give insights into different aspects of the photodissociation of peptides and to probe the conformation of proteins. It is a current question whether the fragmentation pathways are sensitive toward effects of conformational isomerism, tautomerism, and intramolecular interactions in gas-phase peptides.

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.

Site-Selective Dissociation upon Sulfur L-Edge X-ray Absorption in a Gas-Phase Protonated Peptide.

Site-selective dissociation induced by core photoexcitation of biomolecules is of key importance for the understanding of radiation damage processes and dynamics and for its promising use as "chemical scissors" in various applications. However, identifying products of site-selective dissociation in large molecules is challenging at the carbon, nitrogen, and oxygen edges because of the high recurrence of these atoms and related chemical groups. In this paper, we present the observation of site-selective dissociation at the sulfur L-edge in the gas-phase peptide methionine enkephalin, which contains only a single sulfur atom.

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 Al, Si, Si, and Si are proposed on this basis.

Optical properties of size selected neutral Ag clusters: electronic shell structures and the surface plasmon resonance.

We present optical absorption spectra from the ultraviolet to the visible for size selected neutral Agn clusters (n = 5-120) embedded in solid Ne. We compare the spectra to time-dependent density functional calculations (TDDFT) that address the influence of the Ne matrix. With increasing size, several highly correlated electron excitations gradually develop into a single surface plasmon.

Are zinc clusters really amorphous? A detailed protocol for locating global minimum structures of clusters.

We report the results of a conjoint experimental/theoretical effort to assess the structures of free-standing zinc clusters with up to 73 atoms. Experiment provides photoemission spectra for ZnN- cluster anions, to be used as fingerprints in structural assessment, as well as mass spectra for both anion and cation clusters. Theory provides both a detailed description of a novel protocol to locate global minimum structures of clusters in an efficient and reliable way, and its specific application to neutral and charged zinc clusters.