Detection of NO traces Using resonantly enhanced multiphoton ionization: A method for monitoring atmospheric pollutants

Resonantly enhanced multiphoton ionization (REMPI) is proposed as an ultrasensitive detection method forreal-time monitoring of atmospheric pollutants in situ. The technique is demonstrated in the laboratory for NO diluted in pure nitrogen at 560 mbar. The MPI current resulting from (2+1) photon ionization of NO via the resonantC ² H (v=0) state has been measured for several NO concentrations. Detection levels as low as 50 ppt have been obtained.Laboratoire associé à l'Université de Paris-Sud     

Effect of various adsorbates in dephasing and population decay of the Cu(1 0 0) image potential states

A theoretical study of the electron dynamics in image potential states on Cu(1 0 0) surfaces with different types of adsorbates is presented. Scattering of the image state electron by an adsorbate induces inter-band and intra-band transitions leading respectively to the population decay and to the dephasing of the image state. We compare results obtained with low coverage (typically 1 adsorbate atom per 1000 surface atoms) Cs, Ar, and a model electronegative adsorbates. As follows from our results, Cs adsorbates lead to both appreciable dephasing and decay, while electronegative adsorbates mostly affect the dephasing rate. The effect of low coverage Ar adsorbates is small, consistent with their neutrality.     

Modelling of interferometric multiphoton photoemission

A new interferometric multi-photon photoemission scheme has been recently introduced by Güdde et al. [1] and applied to a study of the n=1 image state on Cu(100). We report on the results of a theoretical modelling of this photoemission scheme based on a wave function representation. It incorporates both resonant transitions and two-photon non-resonant transitions. In the case of the n=1 image state on Cu(100), the initial state of the photoemission belongs to a continuum. Summation of the contributions to the photoemission yield from the various initial states is shown to drastically blur the interference structure, acting as an efficient dephasing process. The sensitivity of the new scheme and of the one-colour TR-2PPE scheme to the system dynamical properties is discussed. PACS 73.20.-r; 78.47.+p; 79.60.-i; 82.53.Kp; 42.50.Md     

Edge-forwarding index of star graphs and other Cayley graphs

We present a technique for building, in some Cayley graphs, a routing for which the load of every edge is almost the same. This technique enables us to find the edge-forwarding index of star graphs and complete-transposition graphs.     

H− Formation in proton-metal collisions

Negative hydrogen ion formation is studied by scattering protons from a cesiated tungsten (110) surface. The primary energy ranges from 50 to 400 eV. The angle of incidence is 70° with respect to the surface normal. A maximum conversion efficiency $\text{H}{}^{\mathrm{?}}\text{(H}{}^{\mathrm{?}}\text{+ H}{}^0\text{)}$ of 67% is measured. The measurements can be described in terms of the probability model. The perturbation of the H^? ion by the metal is described within first order perturbation theory. A reasonable agreement between theory and experiment is obtained.     

193 nm photolysis of CHCl3: Probe of the CH product by CRDS

The CH radical production induced by 193 nm two-photon photolysis of CHCl₃ has been measured for the first time via the cavity ring-down absorption spectroscopy of its A–X bands, using a commercial nanosecond pulsed dye laser. The range of pressure and laser intensity, as well as the time window detection, have been carefully chosen to ensure a constant CH number density during the measurement and to avoid post-photolysis reactivity. Internal energy distribution of the CH(X²II) fragment has been derived from population distribution simulations, leading to an average vibrational temperature T_vib = 1900 ± 50 K and rotational temperature T_rot = 300 ± 20 K. Two competing mechanisms can be invoked for the CH production channel: either two-photon absorption via resonant excited states of CHCl₃ leading to dissociation of excited CHCl₃, or two-photon sequential dissociation via the formation of the vibrationally excited CHCl₂ fragment. The latter mechanism is proposed to be the prominent process for CH formation.     

Excitation of local magnetic moments by tunneling electrons

The advent of milli-kelvin scanning tunneling microscopes (STM) with inbuilt magnetic fields has opened access to the study of magnetic phenomena with atomic resolution at surfaces. In the case of single atoms adsorbed on a surface, the existence of different magnetic energy levels localized on the adsorbate is due to the breaking of the rotational invariance of the adsorbate spin by the interaction with its environment, leading to energy terms in the meV range. These structures were revealed by STM experiments in IBM Almaden in the early 2000s for atomic adsorbates on CuN surfaces. The experiments consisted in the study of the changes in conductance caused by inelastic tunneling of electrons (IETS, inelastic electron tunneling spectroscopy). Manganese and Iron adatoms were shown to have different magnetic anisotropies induced by the substrate. More experiments by other groups followed up, showing that magnetic excitations could be detected in a variety of systems: e.g. complex organic molecules showed that their magnetic anisotropy was dependent on the molecular environment, piles of magnetic molecules showed that they interact via intermolecular exchange interaction, spin waves were excited on ferromagnetic surfaces and in Mn chains, and magnetic impurities have been analyzed on semiconductors. These experiments brought up some intriguing questions: the efficiency of magnetic excitations was very high, the excitations could or could not involve spin flip of the exciting electron and singular-like behavior was sometimes found at the excitation thresholds. These facts called for extended theoretical analysis; perturbation theories, sudden-approximation approaches and a strong coupling scheme successfully explained most of the magnetic inelastic processes. In addition, many-body approaches were also used to decipher the interplay between inelastic processes and the Kondo effect. Spin torque transfer has been shown to be effective in changing spin orientations of an adsorbate in theoretical works, and soon after it was shown experimentally. More recently, the previously mentioned strong coupling approach was extended to treat the excitation of spin waves in atomic chains and the ubiquitous role of electron–hole pair creation in de-exciting spins on surfaces has been analyzed. This review article expounds these works, presenting the theoretical approach by the authors while trying to thoroughly review parallel theoretical and experimental works.     

Long-lived adsorbate states on metal surfaces

It has been shown recently that the peculiarities of the band structure of a metal can qualitatively influence the electron tunnelling between an adsorbate and a metal surface, the so-called resonant charge transfer (RCT). The presence of a projected band gap along the normal to the surface in the case of Cu(111) has been shown to lead to a blocking of the RCT in the case of Cs/Cu(111), resulting in the existence of a very long-lived excited state. Such long-lived states are potentially very important for surface reaction mechanisms invoking a transient state as an intermediate. Various systems: Cs, model M- negative ion of p pi symmetry, CO adsorbed on Cu(111), are investigated in order to determine the conditions for the blocking of the RCT and the existence of long-lived states.     

CH radical production from 248 nm photolysis or discharge-jet dissociation of CHBr3 probed by cavity ring-down absorption spectroscopy

The A-X bands of the CH radical, produced in a 248 nm two-photon photolysis or in a supersonic jet discharge of CHBr(3), have been observed via cavity ring-down absorption spectroscopy. Bromoform is a well-known photolytic source of CH radicals, though no quantitative measurement of the CH production efficiency has yet been reported. The aim of the present work is to quantify the CH production from both photolysis and discharge of CHBr(3). In the case of photolysis, the range of pressure and laser fluences was carefully chosen to avoid postphotolysis reactions with the highly reactive CH radical. The CH production efficiency at 248 nm has been measured to be Phi=N(CH)N(CHBr(3))=(5.0+/-2.5)10(-4) for a photolysis laser fluence of 44 mJ cm(-2) per pulse corresponding to a two-photon process only. In addition, the internal energy distribution of CH(X (2)Pi) has been obtained, and thermalized population distributions have been simulated, leading to an average vibrational temperature T(vib)=1800+/-50 K and a rotational temperature T(rot)=300+/-20 K. An alternative technique for producing the CH radical has been tested using discharge-induced dissociation of CHBr(3) in a supersonic expansion. The CH product was analyzed using the same cavity ring-down spectroscopy setup. The production of CH by discharge appears to be as efficient as the photolysis technique and leads to rotationally relaxed radicals.