Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Bromine metallization studied by X-ray absorption spectroscopy

The experimental data carried out by M?ssbauer and magnetic resonances investigations of the structural phase transitions in K₂ZnCl₄ crystals are discussed by a simple electrostatic model, calculating, the lattice contributions to the local electric potential V(r), electric field intensity E(r) and electric field gradient tensor, (r) and taking into account both the fractional electric point charges and rigid lattice approximations. The validity of the model is proved by a good fit of the computing results and experimental data of quadrupole splitting parameters at K sites obtained by ³⁹K-NMR methods in high temperature incommensurate phase ( Pnam symmetry). The experimental results obtained by M?ssbauer and EPR methods in commensurate phase (Pna2₁ symmetry) of iron and copper doped K₂ZnCl₄ crystals are explained by relaxing the rigid lattice approximation. The insertion of probe ions appear to be done on not-exactly-Zn²⁺ site. Received 3 February 1999 and Received in final form 4 May 1999     

Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

Photoexcited GaAs surfaces studied by transient terahertz time-domain spectroscopy

The transmission characteristics of an air-GaAs interface and the transient absorption and index spectra of the thin, photoexcited surface layer are investigated subsequent to excitation by a femtosecond laser pulse. We find that the total phase change and transmission of a terahertz (THz) probe pulse are dominated by interface effects. This observation has important implications in the interpretation of THz time-domain spectroscopy data of absorbing media. We also observe that the THz pulse apparently arrives at the detector as much as 60 fs earlier when it is transmitted through an optically excited GaAs wafer. This effect is fully explained in terms of a frequency-dependent transmission and phase shift at the air-GaAs interface and is not associated with superluminal propagation.     

Triplet and reversed triplet mechanism CIDEP studied by quenching experiments

Quenching experiments are shown to provide a convenient tool to check for the presence of triplet mechanism (TM) spin polarisation in time-resolved EPR spectra following laser flash photolysis. The effect of the triplet quenchers, trans-1,3-pentadiene, fumaronitrile, azo-tert-butane and azo-n-butane upon the spectra following laser photolysis of acetone/propan-2-ol and benzophenone/propan-2-ol photosystems show that no TM polarisation is present in the former system but emissive TM is present in the latter. Use of 2,2′-azo-bis[isobutryronitrile] produces an anomalous emissive polarisation upon quenching, which is tentatively attributed to a reversed TM in the triplet sensitised azo-compound.     

Structure of cobalt nanoparticles as studied by X-ray absorption spectroscopy

Ab initio modeling is used to analyze the specific near-edge features of the X-ray absorption K spectra of ∼3-nm cobalt nanoparticles. It is established that the observed differences between the spectra of the nanoparticles and those of bulk cobalt samples are due to contribution from atoms of the nanoparticles’ surface layer, the local environment of which is considerably different from that of atoms in the bulk of the nanoparticle. It is also established that the local environment of cobalt atoms in the nanoparticle bulk corresponds to the FCC structure of bulk metal, and the fraction of such atoms is found to be 65 ± 5%.     

Ultrafast reaction dynamics of the complete photo cycle of an indolylfulgimide studied by absorption, fluorescence and vibrational spectroscopy

The reaction dynamics of the complete photo cycle, ring-opening (C → E) and ring-closure (E → C), of N-methyl-(6-bromo-1,2-dimethyl-3-indolyl)fulgimide dissolved in acetonitrile are analysed via steady-state and ultrafast spectroscopy using transient absorption in the UV/VIS and mid-IR complemented by ultrafast fluorescence broad-band spectroscopy with a Kerr-gate setup. For the C → E ring-opening reaction induced by light at ~ 550 nm, a time constant of ~ 3 ps was found for the S₁ decay and the S₀ repopulation. Non-exponential signatures, which occur in the 10 ps time domain, were observed and are assigned to the cooling of hot molecules in the electronic ground state. The E → C reaction dynamics induced by UV-light pulses at 360 nm and 387 nm occur within less than 1 ps and are followed by vibrational cooling on the 10 ps time domain. Thus, both ring-opening and ring-closure reactions are completed within a few picoseconds. From transient IR studies and fluorescence measurements it is concluded that these pericyclic reactions occur from different geometries on the excited state potential energy surface.     

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.     

Movements of matrix-isolated methyl fluoride and isotopic species studied by infrared absorption spectroscopy

Infrared absorption spectra were recorded in the 10-μm region for the three isotopic methyl fluoride molecules ¹²CH₃F, ¹²CD₃F, ¹³CD₃F, in the four rare gas matrices and in nitrogen. The two lowest fundamental modes ν₃ (CF stretching) and ν₆ (bending) have been systematically studied, as well as the ν₂ and ν₅ modes of ¹²CD₃F. Relative intensity measurements show that the weak ν₆ transition is enhanced by the matrix, compared to its gas-phase value. Frequency measurements yield vibrational shifts which can be compared to a theoretical estimate of the ν₃ shift based on the Lennard-Jones-Devonshire cell model. These molecules are almost freely rotating in the matrices and a rotational analysis in the ν₃ region brings out quantitative values of the barrier to free rotation as defined in Devonshire's theory. Frequency and relative intensity measurements are also reported for dimeric species.     

Electronic structure of warm dense copper studied by ultrafast x-ray absorption spectroscopy

We use time-resolved x-ray absorption spectroscopy to investigate the unoccupied electronic density of states of warm dense copper that is produced isochorically through the absorption of an ultrafast optical pulse. The temperature of the superheated electron-hole plasma, which ranges from 4000 to 10?000 K, was determined by comparing the measured x-ray absorption spectrum with a simulation. The electronic structure of warm dense copper is adequately described with the high temperature electronic density of state calculated by the density functional theory. The dynamics of the electron temperature is consistent with a two-temperature model, while a temperature-dependent electron-phonon coupling parameter is necessary.     

4f ground state properties of cerium in AuCu3 intermetallic compounds studied by x-ray absorption spectroscopy

L_III absorption edges of cerium in ternary AuCu₃ compounds Ce(Pd_1?xM_x)₃ (M = Ag and Rh) and (Ce_1?xY_x)Pd₃ are presented. We find that Ce in these compounds is mixed valent with n_f ? 0.7. The valence V of Ce(Pd_1?xRh_x)₃ becomes concentration independent of V = 3.29 ± 0.02 for x ? 0.18. In Ce_1?xY_xPd₃ we observe the valence to increase up to V = 3.32 ± 0.02 at the highest concentration of Y. We show, that a critical volume, available for the Ce atom, is associated with the concentration independent valence around 3.3. For both systems, linewidths W₁, W₀ and Δ = E(4f¹) ? E(4f⁰), as derived from L_III double-bump structure, are given. Possible falsifications due to “final states effects” on the valence are discussed.     

Electron irradiation of ion-implanted n-type Si-SiO2 structures studied by deep-level transient spectroscopy

2 structures implanted with 50-keV boron ions is studied by deep-level transient spectroscopy (DLTS) measurements. The DLTS spectra of ion-implanted samples exhibit one peak which corresponds to a deep level located in the forbidden gap of the silicon matrix at E_c-0.40 eV below the conducting band edge. New additional shallower levels are found in the spectra following bombardment by high-energy electrons, the peak intensity being dependent on the irradiation dose. The corresponding activation energy of the created defects, the density of the traps, and the electron-capture cross sections are evaluated. Received: 27 October 1997/Accepted: 8 December 1997     

Oxidation of ZrAl and Zr3Al compounds studied by181Ta-PAC spectroscopy

Hyperfine Interactions - The perturbed angular correlation method was applied to follow the oxidation processes in ZrAl and Zr3Al intermetallic compounds. It was found that the limiting temperature...     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

Comparison of electronic structures of orthorhombic and hexagonal manganites studied by X-ray absorption spectroscopy

Electronic structures of orthorhombic perovskite-type manganites (OM) and hexagonal manganites (HM) are compared by using X-ray absorption near edge structure spectroscopy. This study reveals that the environments around Mn and O ions in both the systems are different. These are reflected primarily in the lifting of degeneracy of the Mn 3d orbitals. Interestingly, the unoccupied Mn 3dx²−y² orbital in HM is strongly hybridized with O 2p states and appears to be responsible for both long range orderings: ferroelectric ordering at high temperatures and ferromagnetic ordering at low temperatures.     

Identification of minority compounds in natural ilmenites by X-ray absorption spectroscopy

Natural ilmenites are used all over the world as raw materials in white pigment (TiO₂) production. Besides the FeTiO₃ in the raw material many other compounds are present. The chemical compounds based on the minority elements influence quality of the final product and are difficult to identify. The knowledge about chemical bonding of the minor elements enables to properly adjust chemical reactions during production processes and to improve quality of the final product. In this paper the X-ray absorption spectroscopy (XAS) identification of the chemical compounds formed by Mg, Mn and Cr in natural ilmenites originating from different places is presented.     

Femtosecond multicolor transient absorption spectroscopy of colloidal silver nanoparticles

Time-resolved femtosecond multicolor absorption spectroscopy of silver nanoparticle (NP) colloids with particle diameter in range of 10–30 nm is presented. The amplified femtosecond excitation of the surface plasmon resonance band resulted in transient absorption spectra reflecting the electron-phonon relaxation dynamics, which takes place on the early picosecond time scale. The monitored band with enhanced absorption in the 490–540 nm spectral range exhibited red-shift with increasing pump fluency from 0.4 mJ/cm² to the 1.5 mJ/cm² level. The growth of the relaxation time with increasing pump fluency reveals the temperature dependent relaxation dynamics caused by the nanometer sized electron confinement in the case of silver. This effect was confirmed also by identification of the relaxation time dependence on the particle diameter at constant pump fluency. The complex experimental results revealed nonlinearities both in the laser excitation and electron relaxation processes.