Ultrafast core-hole-induced dynamics in water probed by x-ray emission spectroscopy

The isotope effect and excitation-energy dependence have been measured in the oxygen K-edge x-ray emission spectrum (XES). The use of XES to monitor core decay processes provides information about molecular dynamics (MD) on an ultrafast time scale through the O1s lifetime of a few femtoseconds. Different nuclear masses give rise to differences in the dynamics and the observed isotope effect in XES is direct evidence of the importance of such processes. MD simulations show that even the excitation-energy dependence in the XES is mainly related to differences in core-excited-state dynamics.     

BaVS3 probed by V L edge x-ray absorption spectroscopy

Polarization dependent vanadium L edge x-ray absorption spectra of BaVS(3) single crystals are measured in the four phases of the compound. The difference between signals with the polarizations E perpendicular to c and E is parallel to c (linear dichroism) changes with temperature. Besides increasing the intensity of one of the maxima, a new structure appears in the pre-edge region below the metal-insulator transition. More careful examination brings to light that the changes start already with pretransitional charge density wave fluctuations. Simple symmetry analysis suggests that the effect is related to rearrangements in the E(g) and A(1g) states, and is compatible with the formation of four inequivalent V-sites along the V-S chain.     

Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by x-ray absorption spectroscopy

We report a comprehensive study of the defects in room-temperature ferromagnetic (RTFM) Cu-doped ZnO thin films using x-ray absorption spectroscopy. The films are doped with 2 at.% Cu, and are prepared by reactive magnetron sputtering (RMS) and pulsed laser deposition (PLD), respectively. The results reveal unambiguously that atomic point defects exist in these RTFM thin films. The valence states of the Cu ions in both films are 2(+). In the film prepared by PLD, the oxygen vacancies (V(O)) form around both Zn ions and Cu ions in the hexagonal wurtzite structure. Upon annealing of the film in O(2), the V(O) population reduces and so does the RTFM. In the film prepared by RMS, the V(O)s around Cu ions are not detected, and the V(O) population around Zn ions is also smaller than in the PLD-prepared film. However, zinc vacancies (V(Zn)) are evidenced. Given the low doping level of spin-carrying Cu ions, these results provide strong support for defect-mediated ferromagnetism in Cu-doped ZnO thin films.     

Nearest-neighbor configuration in (GaIn)(NAs) probed by x-ray absorption spectroscopy

Ga(1-x)In(x)N(y)As(1-y) is a promising material system for the fabrication of inexpensive "last-mile" optoelectronic components. However, details of its atomic arrangement and the relationship to observed optical properties is not fully known. Particularly, a blueshift of emission wavelength is observed after annealing. In this work, we use x-ray absorption fine structure to study the chemical environment around N atoms in the material before and after annealing. We find that as-grown molecular beam epitaxy material consists of a nearly random distribution of atoms, while postannealed material shows segregation of In toward N. Ab initio simulations show that this short-range ordering creates a more thermodynamically stable alloy and is responsible for blueshifting the emission.     

Bonding in liquid carbon studied by time-resolved x-ray absorption spectroscopy

Even the most basic properties of liquid carbon have long been debated due to the challenge of studying the material at the required high temperature and pressure. Liquid carbon is volatile and thus inherently transient in an unconstrained environment. In this paper we use a new technique of picosecond time-resolved x-ray absorption spectroscopy to study the bonding of liquid carbon at densities near that of the solid. As the density of the liquid increases, we see a change from predominantly sp-bonded atomic sites to a mixture of sp, sp2, and sp3 sites and compare these observations with molecular dynamics simulations.     

d-d excitations in manganites probed by resonant inelastic x-ray scattering

We report a study of electronic excitations in manganites exhibiting a range of ground states, using resonant inelastic x-ray scattering (RIXS) at the Mn K edge. Excitations with temperature dependent changes correlated with the magnetism were observed as high as 10 eV. By calculating Wannier functions, and finite-q response functions, we associate this dependence with intersite d-d excitations. The calculated dynamical structure factor is found to be similar to the RIXS spectra.     

Properties of liquid silicon observed by time-resolved x-ray absorption spectroscopy

Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.     

Single and double orbital excitations probed by resonant inelastic x-ray scattering

The dispersion of the elusive elementary excitations of orbital ordered systems, orbitons, has escaped detection so far. The recent advances in resonant inelastic x-ray scattering (RIXS) techniques have made it, in principle, a powerful new probe of orbiton dynamics. We compute the detailed traces that orbitons leave in RIXS for an e{g} orbital ordered system, using the ultrashort core-hole lifetime expansion for RIXS. We observe that both single- and double-orbiton excitations are allowed, where the former, at lower energy, have sharper features. The rich energy- and momentum-dependent intensity variations that we observe make clear that RIXS is an ideal method to identify and map out orbiton dispersions.     

Isotope analysis by infrared laser absorption spectroscopy

The feasibility of IR laser spectroscopy as a technique for the measurement of small abundances of stable and radioactive isotopes has been examined. Theoretical considerations and first experimental results with two laser systems are presented: 1) Coincidences between emission lines of a CO₂-laser and absorption lines of¹³C-substituted ethylene can be used to determine the¹³C-concentration of C₂H₄. 2) A tunable PbS-diode laser emitting in the 4.3 μm-spectral region of the rotation-vibration bands of CO₂ can be used to determine abundances of¹²C,¹³C,¹⁶O,¹⁷O and¹⁸O in small samples of CO₂. With optimized performance, sensitivities up to 10⁻⁹–10⁻¹⁰ seem possible, and for higher abundances an accuracy of 10⁻³. This should allow geophysical isotope studies to be performed and it is hoped that the technique will eventually be applicable to measuring the activity of long-lived radioisotopes.     

Persistence of covalent bonding in liquid silicon probed by inelastic x-ray scattering

Metallic liquid silicon at 1787 K is investigated using x-ray Compton scattering. An excellent agreement is found between the measurements and the corresponding Car-Parrinello molecular dynamics simulations. Our results show persistence of covalent bonding in liquid silicon and provide support for the occurrence of theoretically predicted liquid-liquid phase transition in supercooled liquid states. The population of covalent bond pairs in liquid silicon is estimated to be 17% via a maximally localized Wannier function analysis. Compton scattering is shown to be a sensitive probe of bonding effects in the liquid state.     

Observing photochemical transients by ultrafast x-ray absorption spectroscopy

Accurate determination of the transient electronic structures, which drive photochemical reactions, is crucial in chemistry and biology. We report the detection of transient chemical changes on the picosecond time scale by x-ray-absorption near-edge structure of photoexcited aqueous [Ru(bpy)(3)](2+). Upon ultrashort laser pulse excitation a charge transfer excited state having a 300 ns lifetime is formed. We detect the change of oxidation state of the central Ru atom at its L3 and L2 edges, at a temporal resolution of 100 ps with the zero of time unambiguously determined.     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Frequency shifts in emission and absorption by resonant systems ot two-level atoms

The frequency shifts in emission and absorption arising from resonant many-body interactions in a system of two-level atoms are discussed from several points of view: (1) in the language of superradiance, Dicke states, quantum electrodynamics and perturbation theory; (2) in the classical-path treatment of gaseous emission, with emphasis on the impact approximation; (3) by means of diagrams related to the temperature-Green's function formalism; (4) in the semiclassical model using the macroscopic Bloch vector; (5) through ordinary classical electromagnetic theory in a linear medium.