Surface chemistry of CN bond formation from carbon and nitrogen atoms on Pt(111)

The mechanism of CN bond formation from CH3 and NH3 fragments adsorbed on Pt(111) was investigated with reflection absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). The surface chemistry of carbon-nitrogen coupling is of fundamental importance to catalytic processes such as the industrial-scale synthesis of HCN from CH4 and NH3 over Pt. Since neither CH4 nor NH3 thermally dissociate on Pt(111) under ultrahigh vacuum (UHV) conditions, the relevant surface intermediates were generated through the thermal decomposition of CH3I and the electron-induced dissociation of NH3. The presence of surface CN is detected with TPD through HCN desorption as well as with RAIRS through the appearance of the vibrational features characteristic of the aminocarbyne (CNH2) species, which is formed upon hydrogenation of surface CN at 300 K. The RAIRS results show that HCN desorption at approximately 500 K is kinetically limited by the formation of the CN bond at this temperature. High coverages of Cads suppress CN formation, but the results are not influenced by the coadsorbed I atoms. Cyanide formation is also observed from the reaction of adsorbed N atoms and carbon produced from the dissociation of ethylene.     

Identification and hydrogenation of C2 on Pt(111)

Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to identify the molecular species formed upon the reaction of hydrogen with surface carbon that is deposited by exposing acetylene to a Pt(111) surface held at 750 K. At this temperature, the acetylene is completely dehydrogenated and all hydrogen is desorbed from the surface. Upon subsequent hydrogen exposure at 85 K followed by sequential annealing to higher temperatures, ethylidyne (CCH3), ethynyl (CCH), and methylidyne (CH) are formed. The observation of these species indicates that carbon atoms and C2 molecules exist as stable species on the surface over a wide range of temperatures. Through a combination of RAIRS intensities, hydrogen TPD peak areas, and Auger electron spectroscopy, quantitative estimates of the coverages of the various species were obtained. It was found that 79% of the acetylene-derived carbon was in the form of C2 molecules, with the remainder in the form of carbon atoms. Essentially all of the acetylene-derived carbon could be hydrogenated. In contrast, 85% of an equivalent coverage of carbon deposited by ethylene exposure at 750 K was found to be inert toward hydrogenation.     

Learning to Ignore Online Help Requests

Email discussion groups provide a useful way of organizing email communities with a common interest in a certain topic. Emails submitted to the discussion group are sent automatically to each individual member, thereby eliminating the need to send multiple emails. This method may present unexpected difficulties however, when it comes to cooperation between members. An experimental study shows that email requests for help sent through discussion groups received less responses than emails sent individually to members of a group. Furthermore, subscribers to large discussion groups responded less often to help requests, whether they were sent to the group as a whole or to individuals. These results are discussed in terms of the separate roles of social cues and experience on the diffusion of responsibility effect.     

Analysis of nonlinear gain-induced effects on short-pulse amplification in doped fibers by use of an extended power equation

Optical pulse amplification in doped fibers is studied using an extended power transport equation for the coupled pulse spectral components. This equation includes the effects of gain saturation, gain dispersion, fiber dispersion, fiber nonlinearity, and amplified spontaneous emission. The new model is employed to study nonlinear gain-induced effects on the spectrotemporal characteristics of amplified subpicosecond pulses, in both the anomalous and the normal dispersion regimes.     

Charges as integrals over densities: An alternative formulation of Coleman's theorem

The charge operator is hermitean if and only if the vacuum is invariant. In that case the charge must be invariant under time translations.     

Charges as null plane integrals over tensor densities

For the purpose of defining null plane charges, densities transforming as tensors under the Lorentz group are classified as very good, good, bad and very bad. In the general case of nonconserved tensors in a theory with interaction, it is argued that, in the presence of a mass gap, null plane integrals of members of the first two classes are expected to define symmetric charge operators on dense sets of states; for the last two classes they are not. The existence of null plane charges depends on the asymptotic behavior of off mass shell scattering amplitudes. It is shown that s 1n s behavior is the maximal growth consistent with the existence of null plane charges associated with currents.Supported in part by the U.S.-Israel Binational Science Foundation (B.S.F.), Jerusalem, Israel.     

Mass splitting in relativistic quantum field theory

Null plane integrals of certain classes of tensor densities, conserved or non-conserved, may define symmetric operators on dense subspaces of the in and out states. These operators annihilate the vacuum and may satisfy a Lie algebra. In particular, the possibility that a finite number of null plane charges, which includes the Poincaré generators, close on an algebra whose irreducible representations contain particles with different masses is considered. The situation in which the Lie algebra is defined on a dense domain which is not from the in and out states is discussed. Some algebraic hypotheses other than that of a Lie algebra in the usual sense are briefly considered; in these cases there can be no mass splitting.Supported in part by the U.S.-Israel Binational Science Foundation (B.S.F.), Jerusalem, Israel.