Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L3-edge Puzzle

The Ce L₃ edge XAS spectra of CeO₂ and cerocene [Ce(C₈H₈)₂] were calculated with relativistic ab-initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades-long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core-excited states (ESs). CeO₂ and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f-shell occupations and the value derived from XAS measurements using peak areas (n_f). The identity of the two-peaked Ce L₃ edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f¹ vs. 4f⁰ sub-configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f² sub-configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining n_f from Ce L₃-edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of n_f by calculations, is stressed.     

Degradation kinetics of poly(lactic-co-glycolic) acid block copolymer cast films in phosphate buffer solution as revealed by infrared and Raman spectroscopies

Poly(lactic-co-glycolic) acid (PLGA) is an important copolymer used in drug delivery platforms where controlled release is required. In this work we investigated the in vitro degradation of four PLGA copolymers with L/G molar compositions of 50/50, 65/35, 75/25 and 95/5. ATR-IR and Raman spectroscopies were used to differentiate and quantify the degradation rates of glycolic and lactic units. Both techniques were used to determine the polymer composition as a function of degradation time and the degradation rate constants for the hydrolysis of glycolic and lactic units were calculated using a 1st order kinetics approach. Our results revealed a two stage process for the degradation of PLGA cast films in PBS in agreement with our previous work. The degradation rate constant for glycolic unit was found to be 1.3 times higher than for lactic units. In addition the degradation rate constants for L and G units were shown to decrease proportionally with increasing initial lactic content of the copolymer used to prepare the films.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

Abstract

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Prime radicals in sandwich near-rings

In a previous work [3], the current author, together with P. R. Hall, studied various kinds of primeness in near-rings and sandwich near-rings of continuous functions. In this paper, we study various prime radicals for sandwich near-rings. In certain cases, complete characterisations of the prime, 3-prime, equiprime and strongly equiprime radicals are obtained.     

The reactions of diaminomaleonitrile with isocyanates and either aldehydes or ketones revisited.

A reinvestigation of the reactions of urea derivatives of diaminomaleonitrile 2 with aldehydes or ketones in the presence of triethylamine has established that the products of these reactions are not pyrimidino[5,4-d]pyrimidines 9 as previously reported, but 8-oxo-6-carboxamido-1,2-dihydropurines 12, which are oxidized rapidly in air to the corresponding 6-carboxamidopurines 13. Similarly, the reaction of Schiff base derivatives of DAMN 5 with isocyanates in the presence of triethylamine gives the substituted 2-oxoimidazoles 20 and not the pyrimidine derivatives 8 as previously claimed. The compounds 20 cyclize in solution and are easily oxidized to 8-oxopurine-6-carbonitriles 22, which give the same 8-oxopurine-6-carboxamides 13 upon further hydrolysis.     

Measurement and simulations of hollow atom X-ray spectra of solid-density relativistic plasma created by high-contrast PW optical laser pulses

K-shell spectra of solid Al excited by petawatt picosecond laser pulses have been investigated at the Vulcan PW facility. Laser pulses of ultrahigh contrast with an energy of 160 J on the target allow studies of interactions between the laser field and solid state matter at 10²⁰ W/cm². Intense X-ray emission of KK hollow atoms (atoms without n = 1 electrons) from thin aluminum foils is observed from optical laser plasma for the first time. Specifically for 1.5 μm thin foil targets the hollow atom yield dominates the resonance line emission. It is suggested that the hollow atoms are predominantly excited by the impact of X-ray photons generated by radiation friction to fast electron currents in solid-density plasma due to Thomson scattering and bremsstrahlung in the transverse plasma fields. Numerical simulations of Al hollow atom spectra using the ATOMIC code confirm that the impact of keV photons dominates the atom ionization. Our estimates demonstrate that solid-density plasma generated by relativistic optical laser pulses provide the source of a polychromatic keV range X-ray field of 10¹⁸ W/cm² intensity, and allows the study of excited matter in the radiation-dominated regime. High-resolution X-ray spectroscopy of hollow atom radiation is found to be a powerful tool to study the properties of high-energy density plasma created by intense X-ray radiation.