The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed

Generation of two-photon EPR and Wstates

In this paper we present a scheme for generation of two-photon EPR and W states in the cavity QED context. The scheme requires only one three-level Rydberg atom and two or three cavities. The atom is sent to interact with cavities previously prepared in vacuum states, via two-photon process. An appropriate choice of the interaction times one obtains the mentioned state with maximized fidelities. These specific times and the values of success probability and fidelity are discussed.Comment: 4 pages, 5 figure

Molecular systematic perspectives on biome origins and dynamics

invited commentary on the following article:De-Nova JA, Medina R, Montero JC, Weeks A, Rosell JA, Olson ME, Eguiarte LE, Magallo ́n S. 2011. Insights into the historical construction of species-rich Mesoamerican seasonally dry tropical forests: the diversification of Bursera (Burseraceae, Sapindales). New Phytologist 193: 276–287.Phylogenetic reconstructions of diverse tropical groups have yielded biological insights that extend well beyond the field of systematics, illuminating such topics as biome assembly and plant–insect coevolution. In this issue of New Phytologist, De-Nova et al. (pp. 276–287) present a rigorous time-calibrated phylogeny of the Neotropical tree genus Bursera in order to estimate lineage ages, and to investigate how geography and ecology have structured its species diversification. Because Bursera is a dominant component of Mesoamerican seasonally dry tropical forests (SDTFs), the study provides evidence relating to the origin and expansion of this important biome. The study also sets the record straight on the age of a well-known plant– herbivore interaction.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/88158/1/Dick&Pennington2012.pdf-

Controlling a mobile robot with a biological brain

The intelligent controlling mechanism of a typical mobile robot is usually a computer system. Some recent research is ongoing in which biological neurons are being cultured and trained to act as the brain of an interactive real world robot�thereby either completely replacing, or operating in a cooperative fashion with, a computer system. Studying such hybrid systems can provide distinct insights into the operation of biological neural structures, and therefore, such research has immediate medical implications as well as enormous potential in robotics. The main aim of the research is to assess the computational and learning capacity of dissociated cultured neuronal networks. A hybrid system incorporating closed-loop control of a mobile robot by a dissociated culture of neurons has been created. The system is flexible and allows for closed-loop operation, either with hardware robot or its software simulation. The paper provides an overview of the problem area, gives an idea of the breadth of present ongoing research, establises a new system architecture and, as an example, reports on the results of conducted experiments with real-life robots

Non-degenerate four-wave mixing in rubidium vapor: transient regime

We investigate the transient response of the generated light from Four-Wave Mixing (FWM) in the diamond configuration using a step-down field excitation. The transients show fast decay times and oscillations that depend on the detunings and intensities of the fields. A simplified model taking into account the thermal motion of the atoms, propagation, absorption and dispersion effects shows qualitative agreement with the experimental observations with the energy levels in rubidium (5S1/2, 5P1/2, 5P3/2 and 6S1/2). The atomic polarization comes from all the contributions of different velocity classes of atoms in the ensemble modifying dramatically the total transient behavior of the light from FWM.Comment: 11 pages, 11 figures, to be published in Physical Review

Surface states in nearly modulated systems

A Landau model is used to study the phase behavior of the surface layer for magnetic and cholesteric liquid crystal systems that are at or near a Lifshitz point marking the boundary between modulated and homogeneous bulk phases. The model incorporates surface and bulk fields and includes a term in the free energy proportional to the square of the second derivative of the order parameter in addition to the usual term involving the square of the first derivative. In the limit of vanishing bulk field, three distinct types of surface ordering are possible: a wetting layer, a non-wet layer having a small deviation from bulk order, and a different non-wet layer with a large deviation from bulk order which decays non-monotonically as distance from the wall increases. In particular the large deviation non-wet layer is a feature of systems at the Lifshitz point and also those having only homogeneous bulk phases.Comment: 6 pages, 7 figures, submitted to Phys. Rev.

Specific heat amplitude ratios for anisotropic Lifshitz critical behaviors

We determine the specific heat amplitude ratio near a $m$-axial Lifshitz point and show its universal character. Using a recent renormalization group picture along with new field-theoretical $\epsilon_{L}$-expansion techniques, we established this amplitude ratio at one-loop order. We estimate the numerical value of this amplitude ratio for $m=1$ and $d=3$. The result is in very good agreement with its experimental measurement on the magnetic material $MnP$. It is shown that in the limit $m \to 0$ it trivially reduces to the Ising-like amplitude ratio.Comment: 8 pages, RevTex, accepted as a Brief Report in Physical Review

New heterodontosaurid remains from the Canadon Asfalto Formation: cursoriality and the functional importance of the pes in small heterodontosaurids

New ornithischian remains reported here (MPEF-PV 3826) include two complete metatarsi with associated phalanges and caudal vertebrae, from the late Toarcian levels of the Canadon Asfalto Formation. We conclude that these fossil remains represent a bipedal heterodontosaurid but lack diagnostic characters to identify them at the species level, although they probably represent remains of Manidens condorensis, known from the same locality. Histological features suggest a subadult ontogenetic stage for the individual. A cluster analysis based on pedal measurements identifies similarities of this specimen with heterodontosaurid taxa and the inclusion of the new material in a phylogenetic analysis with expanded character sampling on pedal remains confirms the described specimen as a heterodontosaurid. Finally, uncommon features of the digits (length proportions among nonungual phalanges of digit III, and claw features) are also quantitatively compared to several ornithischians, theropods, and birds, suggesting that this may represent a bipedal cursorial heterodontosaurid with gracile and grasping feet and long digits. In particular, the elongated non-terminal pedal phalanges and morphology of digit III resemble features present in arboreal birds, a unique condition found so far among ornithischians

Low GWP Refrigerants for Air Conditioning Applications

Refrigerants with low environmental impact have been developed as replacements for R22 and R410A in air conditioning applications. L-20 and L-41 have been evaluated in representative residential equipment. This study discusses the performance at high ambient temperatures (warm climate) and potential design changes. In addition, 1233zd and 1234ze have been evaluated as replacements for R123 and R134a in low and medium pressure chiller applications. Theoretical and experimental results are discussed in detail showing the benefits of using these new fluids