PECD study of a single-conformer molecule: a critical comparison of experiment and theory.

In this work we address a specific experimental and theoretical question regarding the influence of a conformational population in the modeling of photoelectron circular dichroism (PECD) spectroscopy. In the past two decades, PECD has revealed a rich and complex phenomenology in molecular processes with unprecedented insight, especially in molecular geometry sensitivity. Since the early development of this spectroscopy, theory has pointed out the importance of conformer influence on PECD; in particular, the rotation of methyl groups was surprisingly found to be responsible for strong modulation of the PECD signal. Here, to advance understanding of the effect of rotations, we have chosen to study norcamphor, a single-conformer molecule, as a benchmark for a PECD comparison between experiment and theory at the density functional theory (DFT) and time-dependent density functional theory (TDDFT) levels. The excellent agreement between experimental data and theory for norcamphor sheds light on the influence of rotations and gives a solid explanation for the reasonable qualitative agreement in the PECD of camphor, where three methyl groups are added to the same molecular structure.

Fragmentation dynamics of doubly charged camphor molecule following C 1s Auger decay.

The fragmentation dynamics of the gas-phase, doubly charged camphor molecule, formed by Auger decay following carbon 1s ionisation, using soft X-ray synchrotron radiation, is presented in this work. The technique of velocity map imaging combined with a photoelectron-photoion-photoion coincidence (VMI-PEPIPICO) is used for both electron energy and ion momentum (in-sequence) measurements. The experimental study is complemented by molecular dynamics simulation, performed with an NVT (moles, volume, and temperature) ensemble. Velocity Verlet algorithms were used for time integration at various internal energies. These simulations validate observed dissociation pathways. From these, we successfully deduce that the internal energy of the doubly charged molecular ion has a significant contribution to the fragmentation mechanism. Notably, a prominent signature of the internal energy was observed in the experimentally determined energies of the neutral fragment in these deferred charge separation pathways, entailing a more detailed theoretical study to uncover the exact dissociation dynamics.

Broadband optical ultrafast reflectivity of Si, Ge and GaAs.

Ultrafast optical reflectivity measurements of silicon, germanium, and gallium arsenide have been carried out using an advanced set-up providing intense subpicosecond pulses (35 fs FWHM, [Formula: see text] = 400 nm) as a pump and broadband 340-780 nm ultrafast pulses as a white supercontinuum probe. Measurements have been performed for selected pump fluence conditions below the damage thresholds, that were carefully characterized. The obtained fluence damage thresholds are 30, 20.8, 9.6 mJ/[Formula: see text] for Si, Ge and GaAs respectively. Ultrafast reflectivity patterns show clear differences in the Si, Ge, and GaAs trends both for the wavelength and time dependences. Important changes were observed near the wavelength regions corresponding to the [Formula: see text], [Formula: see text] singularities in the joint density of states, so related to the peculiar band structure of the three systems. For Ge, ultrafast reflectivity spectra were also collected at low temperature (down to 80 K) showing a shift of the characteristic doublet peak around 2.23 eV and a reduction of the recovery times.

Charge Exchange Dominates Long-Range Interatomic Coulombic Decay of Excited Metal-Doped Helium Nanodroplets.

Atoms and molecules attached to rare-gas clusters are ionized by an interatomic autoionization process traditionally termed "Penning ionization" when the host cluster is resonantly excited. Here we analyze this process in the light of the interatomic Coulombic decay (ICD) mechanism, which usually contains a contribution from charge exchange at a short interatomic distance and one from virtual photon transfer at a large interatomic distance. For helium (He) nanodroplets doped with alkali metal atoms (Li, Rb), we show that long-range and short-range contributions to the interatomic autoionization can be clearly distinguished by detecting electrons and ions in coincidence. Surprisingly, ab initio calculations show that even for alkali metal atoms floating in dimples at a large distance from the nanodroplet surface, autoionization is largely dominated by charge-exchange ICD. Furthermore, the measured electron spectra manifest the ultrafast internal relaxation of the droplet mainly into the 1s2s1S state and partially into the metastable 1s2s3S state.

Graphene-Induced Improvements of Perovskite Solar Cell Stability: Effects on Hot-Carriers.

Hot-carriers, that is, charge carriers with an effective temperature higher than that of the lattice, may contribute to the high power conversion efficiency (PCE) shown by perovskite-based solar cells (PSCs), which are now competitive with silicon solar cells. Hot-carriers lose their excess energy in very short times, typically in a few picoseconds after excitation. For this reason, the carrier dynamics occurring on this time scale are extremely important in determining the participation of hot-carriers in the photovoltaic process. However, the stability of PSCs over time still remains an issue that calls for a solution. In this work, we demonstrate that the insertion of graphene flakes into the mesoscopic TiO2 scaffold leads to stable values of carrier temperature. In PSCs aged over 1 week, we indeed observe that in the graphene-free perovskite cells the carrier temperature decreases by about 500 K from 1800 to 1300 K, while the graphene-containing cell shows a reduction of less than 200 K after the same aging time delay. The stability of the carrier temperature reflects the stability of the perovskite nanocrystals embedded in the mesoporous graphene-TiO2 layer. Our results, based on femtosecond transient absorption measurements, show that the insertion of graphene can be beneficial for the design of stable PSCs with the aim of exploiting the hot-carrier contribution to the PCE of the PSCs.

Conformational effects in photoelectron circular dichroism.

Photoelectron circular dichroism (PECD) is a novel type of spectroscopy, which presents surprising sensitivity to conformational effects in chiral systems. While classical photoelectron spectroscopy mainly responds to conformational effects in terms of energy level shifts, PECD provides a rich and detailed response to tiny changes in electronic and structural properties by means of the intensity dispersion of the circular dichroism as a function of photoelectron kinetic energy. In this work, the basics of PECD will be outlined, emphasizing the role of interference from the [Formula: see text] outgoing partial wave of the photoelectron in the PECD transition matrix element, which is responsible for the extreme sensitivity to conformational effects. Examples using molecular systems and interfaces will shed light on the powerful application of PECD to classical conformational effects such as group substitution, isomerism, conformer population and clustering. Moreover, the PECD results will be reported in challenging new fields where conformations play a key role, such as vibrational effects, transient chirality and time- resolved experiments. To date, PECD has mostly been based on synchrotron radiation facilities, but it also has a future as a table-top lab experiment by means of multiphoton ionization. An important application of PECD as an analytical tool will be reported. The aim of this review is to illustrate that in PECD, the presence of conformational effects is essential for understanding a wide range of effects from a new perspective, making it different from classical spectroscopy.

Resonant circular dichroism of chiral metal-organic complex.

A sizable enhancement of the circular dichroism in photoelectron spectroscopy has been measured and computed for the metal complex Δ-cobalt(III) tris-acetylacetonate highest occupied molecular orbital state in the region of the Co 3p→3d Fano resonance. In the resonance the dichroism reaches the maximum value of 5% and even changes its sign as compared to the direct photoionization channel. We ascribe this enhancement to electron correlation processes, namely, with the coupling between discrete excitations and the continuum, which is correctly described in the time dependent density functional theory (TDDFT) framework. These findings open new physical aspects of photoelectron circular dichroism that now can be interpreted not only via the simple direct ionization, but also through more complex electron correlation processes.

The valence electronic structure and conformational flexibility of epichlorohydrin.

The electronic structure of epichlorohydrin is investigated in the whole valence region by a combined experimental and theoretical study. The issue of controversial assignments of the molecular electronic structure is here addressed. Photoelectron spectra (PES) and Threshold Photoelectron spectra (TPES) of room temperature molecules in the gas phase are recorded. Geometries and energies of the stable conformers due to internal rotation of the C-C-C-Cl dihedral angle, gauche-II (g-II), gauche-I (g-I), and cis, are calculated, and the effect of the conformational flexibility on the photoionization energetics is studied by DFT and 2h-1p Configuration Interaction (CI) methods. Strong breakdown of the Koopmans Theorem (KT) is obtained for the four outermost ionizations, which are further investigated by higher level ab initio calculations. The full assignment of the spectrum is put on a firm basis by the combination of experimental and theoretical results. The orbital composition from correlated calculations is found closer to the DFT orbitals, which are then used to analyze the electronic structure of the molecule. The Highest Occupied Molecular Orbital (HOMO) and HOMO--2 are n(O)/n(Cl) mixed orbitals. The nature of each valence MO is generally preserved in all the conformers, although the magnitude of the n(O)/n(Cl) mixing in HOMO and HOMO--2 varies to some extent with the C-C-C-Cl dihedral angle. The low energy part of the HOMO PE band is predicted to be substantially affected by the conformational flexibility, as experimentally observed in the spectra. The rest of the spectrum is described in terms of the dominant conformer g-II, and a good agreement between experiment and theory is found. The inner-valence PE spectrum is characterized by satellite structures, due to electron correlation effects, which are interpreted by means of 2h-1p CI calculations.

Chirality transfer from a single chiral molecule to 2D superstructures in alaninol on the Cu(100) surface.

The formation of 2D chiral monolayers obtained by self-assembly of chiral molecules on surfaces has been widely reported in the literature. Control of chirality transfer from a single molecule to surface superstructures is a challenging and important aspect for tailoring the properties of 2D nanostructures. However, despite the wealth of investigations performed in recent years, how chiral transfer takes place on a large scale still remains an open question. In this paper we report a coupling of scanning tunneling microscopy and low energy electron diffraction measurements with an original theoretical approach, combining molecular dynamics and essential dynamics with density functional theory, to investigate self-assembled chiral structures formed when alaninol adsorbs on Cu(100). The peculiarity of this system is related to the formation of tetrameric molecular structures which constitute the building blocks of the self-assembled chiral monolayer. Such characteristics make alaninol/Cu(100) a good candidate to reveal chiral expression changes. We find that the deposition of alaninol enantiomers results in the formation of isolated tetramers that are aligned along the directions of the substrate at low coverage or when geometrical confinement prevents long-range order. Conversely, a rotation of 14° with respect to the Cu(100) unit vectors is observed when small clusters of tetramers are formed. An insight to the process leading to a 2D globally chiral surface has been obtained by monitoring molecular assemblies as they grow from the early stages of adsorption, suggesting that the distinctive orientation of the self-assembled monolayer originates from a balance of cooperating forces which start acting only when tetramers pack together to form small clusters.

2-amino-1-propanol versus 1-amino-2-propanol: valence band and C 1s core-level photoelectron spectra.

Valence band and C 1s core-level photoelectron spectra of S-(+)-2-amino-1-propanol (alaninol) and S-(+)-1-amino-2-propanol (isopropanolamine) have been studied by means of synchrotron radiation photoelectron spectroscopy in gas phase. The alaninol, the reduced derivative of the alanine, is a good test system of amino acid-like structures. The isopropanolamine, presenting the inversion of the two functional groups of the alaninol at the chiral carbon, offers the opportunity to study the effect of -OH and -NH(2) structural position on the photoelectron spectra. The influence of the conformational contribution on the electronic structure and the photoelectron spectra has been interpreted using density functional and ab initio theoretical calculations. Agreement has been achieved by taking into account the presence, in gas phase, of two conformers with different population ratios in both chiral systems. The C 1s core-level spectra of alaninol and isopropanolamine are reported and the peak positions of the three carbon atoms of the molecules are assigned.

Vibrational state dependence of beta and D asymmetry parameters: the case of the highest occupied molecular orbital photoelectron spectrum of methyl-oxirane.

The beta angular asymmetry and D dichroic asymmetry parameters of the methyl-oxirane highest occupied molecular orbital (HOMO) band have been experimentally investigated with vibrational resolution using synchrotron radiation. A theoretical calculation of the Franck-Condon factors between vibrational ground state and different ionic vibrational states, in the Born-Oppenheimer harmonic approximation, has been performed in order to gain information on the vibrational states mainly involved in the HOMO photoelectron band. The general good agreement between theoretical and experimental results allows a reliable assignment of the major features. The experimental determination of beta and D shows their dependence on the different final vibrational states. This paper reports, for the first time, experimental evidence of the dependence of the dichroic D parameter on the vibrational excitation of the ion.

Spin-flop ordering from frustrated ferro- and antiferromagnetic interactions: a combined theoretical and experimental study of a Mn/Fe(100) monolayer.

The occurrence of a noncollinear magnetic structure at a Mn monolayer grown epitaxially on Fe(100) is predicted theoretically, using spinor density-functional theory, and observed experimentally, using x-ray magnetic circular dichroism (XMCD) and linear dichroism (XMLD) spectroscopies. The combined use of XMCD and XMLD at the Mn-absorption edge allows us to assess the existence of ferromagnetic and antiferromagnetic order at the interface, and also to determine the moment orientations with element specificity. The experimental results thus obtained are in excellent agreement with the magnetic structure determined theoretically.

Valence photoionization dynamics in circular dichroism of chiral free molecules: the methyl-oxirane.

The dynamical behavior of circular dichroism for valence photoionization processes in pure enantiomers of randomly oriented methyl-oxirane molecules has been studied by circularly polarized synchrotron radiation. Experimental results of the dichroism coefficient obtained for valence photoionization processes as a function of photon energy have been compared with theoretical values predicted by state-of-the-art ab initio density-functional theory. The circular dichroism measured at low electron kinetic energies was as large as 11%. Trends in the experimental dynamical behavior of the dichroism coefficients D(i)(omega) have been observed. Agreement between experimental and theoretical results permits unambiguous identification of the enantiomer and of the individual orbitals.

Circular dichroism in angle-resolved photoemission spectra of under- and overdoped Pb-Bi2212.

We use angle-resolved photoemission with circularly polarized excitation to demonstrate that in the 5 x 1 superstructure-free (Pb,Bi)(2)Sr(2)CaCu(2)O(8+delta) (Pb-Bi2212) material there are no signatures of time-reversal symmetry breaking in the sense of the criteria developed earlier [Nature (London) 416, 610 (2002)]]. The dichroic signal retains reflection antisymmetry as a function of temperature and doping and in all mirror planes, precisely defined by the experimental dispersion at low energies. The obtained results demonstrate that the signatures of time-reversal symmetry violation in pristine Bi2212, as determined by angle-resolved photoemission spectroscopy, are not a universal feature of all cuprate superconductors.

Electronic and magnetic structures of Sr(2)FeMoO(6).

We have investigated the electronic and magnetic structures of Sr(2)FeMoO(6) employing site-specific direct probes, namely x-ray absorption spectroscopy with linearly and circularly polarized photons. In contrast to some previous suggestions, the results clearly establish that Fe is in the formal trivalent state in this compound. With the help of circularly polarized light, it is unambiguously shown that the moment at the Mo sites is below the limit of detection (<0.25 mu(B)), resolving a previous controversy. We also show that the decrease of the observed moment in magnetization measurements from the theoretically expected value is driven by the presence of mis-site disorder between Fe and Mo sites.

Diffraction anomalous fine structure of forbidden reflection of super-ordered GaInP.

We used DAFS to probe super-ordered domains in InGaP/GaAs epitaxial growth. The sample was lattice matched InGaP epitaxially grown on GaAs with a substrate miscut angle of 6 degrees with respect to the (001) direction. InGaP epi-layer exhibited (111)-type alloy ordering, of alternating InP and GaP like planes and giving rise to a (-5/2,5/2,-5/2) Bragg peak reflection which becomes allowed. Structural data can be extracted, at the same time, for the surroundings of Gallium in the bulk and in the epi-layer from allowed reflections, while the forbidden reflection gives structural details around Gallium in the ordered domains. Difference with the bulk InGaP Fourier transform confirms the symmetry selectivity of chosen reflections for the super-ordered domains.

[Anti-Pseudomonas aeruginosa antibodies, circulating immune complexes, and anticytoplasm antibodies of neutrophils in patients with cystic fibrosis with and without Pseudomonas aeruginosa colonization]. / Anticorpi anti-Pseudomonas aeruginosa, immunocomplessi circolanti ed anticorpi anticitoplasma dei neutrofili in pazienti affetti da fibrosi cistica colonizzati e non da Pseudomonas aeruginosa.

Chronic lung infections, mainly due to Pseudomonas aeruginosa (Pa), account for the most of the morbidity and mortality in CF patients. The pathogenic factors predisposing to airway colonization are still nuclear. Host's immune response is not only poorly protective but can also act as a damaging factor in the development of the disease. Moreover, clinical manifestations of an overactive immune response, including vasculitis and arthropathy, have been recently described in the CF population. To deepen factors involved in the pathogenesis of lung injury, we evaluated the presence of anti-Pa precipitating antibodies, circulating immune complexes (CIC) and antineutrophil cytoplasmic antibodies (ANCA) in sera from 50 CF patients colonized and not by Pa. Number of anti-Pa precipitins was significantly different in chronically and in not colonized patients (p < 0.001; t = 7.75). Anti-Pa antibodies were positively correlated to age (p = 0.002, r = 0.42) and inversely correlated to lung function parameters (p = 0.031 r = -0.35 with respect to FVC). Mean C3-CIC levels in the sera were statistically higher in chronically colonized patients (p = 0.013; t = 2.57); while there was not a significant difference with respect to C1q-CIC values. Four patients, all chronically colonized by Pa, were ANCA-positive at indirect immunofluorescence, showing a cytoplasmic pattern. All 50 patients were found to be negative when tested for anti-mpo and anti-pr3 antibodies with ELISA. In conclusion, our data demonstrate that persistence of Pa provides a stimulus for chronic inflammation and the immune response in CF patients, leading to anti-Pa antibodies and CIC production. Even in the face of further research, we speculate that c-ANCA production is secondary to neutrophil activation with a consequent release of cytoplasmic enzymes that perpetuate and increase the inflammatory process. Since anti-mpo and anti-pr3 antibodies rarely occur in CF patients we suggest that other antigenic specificities may be involved in ANCA production.

Some anti-thyroperoxidase antibodies positive sera give a pANCA pattern on ethanol-fixed human neutrophils: cross-reactivity or false positives?

Fifty-six sera from patients with autoimmune thyroiditis and 33 sera from patients with MPO-ANCA were examined in order to ascertain whether a cross reactivity between MPO-ANCA and anti-thyroperoxidase (aTPO) was present. Sera from 20 healthy donors aTPO and aMPO negative were used as control. About 95% of heat inactivated sera from patients with autoimmune thyroiditis and from controls gave positive results (atypical pANCA pattern) on ethanol-fixed neutrophils. The prevalence of positive results was significantly lower when unheated aTPO positive sera were used (17.8%). On the other hand, only 9% of sera with MPO-ANCA were positive on cryostatic sections of human thyroid. Indirect immunofluorescence tests (IF) on human neutrophils with MPO defect were negative with sera from patients with MPO-ANCA, but uninactivated sera with aTPO and positive for pANCA on normal neutrophils showed a very high prevalence of positive results (90%). According to our data only few sera positive for aTPO recognize "normal" MPO, but the majority of sera from patients with autoimmune thyroiditis and positive for pANCA on normal neutrophils recognize also an "abnormal" MPO. On the other hand MPO-ANCA usually recognize epitopes presently only on the normal enzyme, a small proportion of these autoantibodies can react with TPO. Heat inactivated sera give false positive results for pANCA on ethanol fixed human neutrophils.

Immunological findings in Kawasaki disease: an evaluation in a cohort of Italian children.

OBJECTIVE: Multiple humoral and cellular abnormalities in Kawasaki disease (KD) have already been described. In this study an analysis of immunological findings in a cohort of 34 Italian children affected with KD is reported, and the potential clinical significance of such alterations in predicting the development of coronary aneurysm and the prognosis of the disease is evaluated. METHODS: Levels of circulating immune complexes (CIC), antinuclear antibodies (ANA), anticardiolipin (aCL), antineutrophil cytoplasmic antibodies (ANCA), and anti-endothelial cells (AECA) and the T cell profile were determined in both the acute and the convalescent phases, and were compared to febrile, sex- and age-matched children. RESULTS: CIC were present in 66% of the patients, 18 of whom were in the acute phase and 13 in the convalescent phase. In the control group CIC were detected in 47% of the children. ANA were negative in both the KD and in the febrile group. ANCA were present in 8%, AECA in 26%, and aCL in 30% of KD patients (IgG aCL antibodies were found in 14 patients, IgM aCL in, 1 and 1 had both). Among the controls, aCL antibodies were found in 5 patients (22%); in particular 1 (4.4%) had IgG and 4 (17.4%) had IgM aCL. An altered T cell profile, with an inverted CD4/CD8 ratio, was found in all KD children. All of the immune alterations showed a lower incidence in the convalescent than in the acute phase. No significant relationship between any of these immune findings and cardiac involvement or any other clinical manifestations was found. CONCLUSION: Our data confirms the previously reported immunological anomalies in KD both in the acute and the convalescent phases, with a decreased incidence of such alterations in the convalescent phase. No prognostic significance for the occurrence of aneurysm could be demonstrated.