Palladacycles: Effective Catalysts for a Multicomponent Reaction with Allylpalladium(II)-Intermediates

Palladium(II) complexes with an auxiliary bidentate ligand featuring one C-Pd bond and a Pd-N-donor bond (palladacycles) have been shown to afford improved yields of homoallylic amines from a three-component coupling of boronic acids, allenes and imines in comparison to the yields of homoallylic amines achieved with the originally reported catalyst (Pd(OAc)2/P(t-Bu)3), thus extending the scope of the reaction. 31P NMR monitoring studies indicate that distinct intermediates featuring Pd-P bonds originate in the reactions catalyzed by either Pd(OAc)2/P(t-Bu)3 or the pallada(II)cycle/P(t-Bu)3 systems, suggesting that the role of the pallada(II)cycles is more complex than just precatalysts. The importance of an additional phosphine ligand in the reactions catalyzed the pallada(II)cycles was established, and its role in the catalytic cycle has been proposed. Insights into the nature of the reactive intermediates that limit the performance of the originally reported catalytic systems has been gained

Mechanical properties of Pt monatomic chains

The mechanical properties of platinum monatomic chains were investigated by simultaneous measurement of an effective stiffness and the conductance using our newly developed mechanically controllable break junction (MCBJ) technique with a tuning fork as a force sensor. When stretching a monatomic contact (two-atom chain), the stiffness and conductance increases at the early stage of stretching and then decreases just before breaking, which is attributed to a transition of the chain configuration and bond weakening. A statistical analysis was made to investigate the mechanical properties of monatomic chains. The average stiffness shows minima at the peak positions of the length-histogram. From this result we conclude that the peaks in the length-histogram are a measure of the number of atoms in the chains, and that the chains break from a strained state. Additionally, we find that the smaller the initial stiffness of the chain is, the longer the chain becomes. This shows that softer chains can be stretched longer.Comment: 6 pages, 5 figure

Lectures on the Asymptotic Expansion of a Hermitian Matrix Integral

In these lectures three different methods of computing the asymptotic expansion of a Hermitian matrix integral is presented. The first one is a combinatorial method using Feynman diagrams. This leads us to the generating function of the reciprocal of the order of the automorphism group of a tiling of a Riemann surface. The second method is based on the classical analysis of orthogonal polynomials. A rigorous asymptotic method is established, and a special case of the matrix integral is computed in terms of the Riemann $\zeta$-function. The third method is derived from a formula for the $\tau$-function solution to the KP equations. This method leads us to a new class of solutions of the KP equations that are \emph{transcendental}, in the sense that they cannot be obtained by the celebrated Krichever construction and its generalizations based on algebraic geometry of vector bundles on Riemann surfaces. In each case a mathematically rigorous way of dealing with asymptotic series in an infinite number of variables is established

Final Report for: "Bis-pi-allylpalladium Complexes in Catalysis of Multicomponent Reactions"

The research project involved the development of new and functionally improved Pd(II) catalyst for a three-component reaction of boronic acids, allenes and imines to afford homoallylic amines that are useful in synthesis of biologically active heterocycles. Furthermore, insights into the reaction mechanism and the structure and reactivity of the catalytically active intermediates involved in this process were sought. As a result of this work, a new type of Pd-catalysts possessing an auxiliary ligand attached to the Pd center via a C-Pd and N-Pd bonds were identified, and found to be more active than the traditional catalysts derived from Pd(OAc)2. The new catalysts provided an access to a broader range of homoallylic amine products. Although the final unequivocal evidence regarding the structure of the Pd(II) complex involved in the nucleophilic transfer of the allyl fragment from the palladium center to the imine could not be obtained, mechanistic insights into the events that are detrimental to the activity of the originally reported Pd(OAc)2-based catalytic systems were uncovered

Three Dimensional Structure and Energy Balance of a Coronal Mass Ejection

The Ultraviolet Coronagraph Spectrometer (UVCS) observed Doppler shifted material of a partial Halo Coronal Mass Ejection (CME) on December 13 2001. The observed ratio of [O V]/O V] is a reliable density diagnostic important for assessing the state of the plasma. Earlier UVCS observations of CMEs found evidence that the ejected plasma is heated long after the eruption. We have investigated the heating rates, which represent a significant fraction of the CME energy budget. The parameterized heating and radiative and adiabatic cooling have been used to evaluate the temperature evolution of the CME material with a time dependent ionization state model. The functional form of a flux rope model for interplanetary magnetic clouds was also used to parameterize the heating. We find that continuous heating is required to match the UVCS observations. To match the O VI-bright knots, a higher heating rate is required such that the heating energy is greater than the kinetic energy. The temperatures for the knots bright in Ly$\alpha$ and C III emission indicate that smaller heating rates are required for those regions. In the context of the flux rope model, about 75% of the magnetic energy must go into heat in order to match the O VI observations. We derive tighter constraints on the heating than earlier analyses, and we show that thermal conduction with the Spitzer conductivity is not sufficient to account for the heating at large heights.Comment: 40 pages, 16 figures, accepted for publication in ApJ For associated mpeg file, please see https://www.cora.nwra.com/~jylee/mpg/f5.mp

Functional representation of the Ablowitz-Ladik hierarchy

The Ablowitz-Ladik hierarchy (ALH) is considered in the framework of the inverse scattering approach. After establishing the structure of solutions of the auxiliary linear problems, the ALH, which has been originally introduced as an infinite system of difference-differential equations is presented as a finite system of difference-functional equations. The representation obtained, when rewritten in terms of Hirota's bilinear formalism, is used to demonstrate relations between the ALH and some other integrable systems, the Kadomtsev-Petviashvili hierarchy in particular.Comment: 15 pages, LaTe

The Grad-Shafranov Reconstruction of Toroidal Magnetic Flux Ropes: Method Development and Benchmark Studies

We develop an approach of Grad-Shafranov (GS) reconstruction for toroidal structures in space plasmas, based on in-situ spacecraft measurements. The underlying theory is the GS equation that describes two-dimensional magnetohydrostatic equilibrium as widely applied in fusion plasmas. The geometry is such that the arbitrary cross section of the torus has rotational symmetry about the rotation axis $Z$, with a major radius $r_0$. The magnetic field configuration is thus determined by a scalar flux function $\Psi$ and a functional $F$ that is a single-variable function of $\Psi$. The algorithm is implemented through a two-step approach: i) a trial-and-error process by minimizing the residue of the functional $F(\Psi)$ to determine an optimal $Z$ axis orientation, and ii) for the chosen $Z$, a $\chi^2$ minimization process resulting in the range of $r_0$. Benchmark studies of known analytic solutions to the toroidal GS equation with noise additions are presented to illustrate the two-step procedures and to demonstrate the performance of the numerical GS solver, separately. For the cases presented, the errors in $Z$ and $r_0$ are 9$^\circ$ and 22\%, respectively, and the relative percent error in the numerical GS solutions is less than 10\%. We also make public the computer codes for these implementations and benchmark studies.Comment: submitted to Sol. Phys. late Dec 2016; under review; code will be made public once review is ove

Numerical Investigation of a Coronal Mass Ejection from an Anemone Active Region: Reconnection and Deflection of the 2005 August 22 Eruption

We present a numerical investigation of the coronal evolution of a coronal mass ejection (CME) on 2005 August 22 using a 3-D thermodynamics magnetohydrodynamic model, the SWMF. The source region of the eruption was anemone active region (AR) 10798, which emerged inside a coronal hole. We validate our modeled corona by producing synthetic extreme ultraviolet (EUV) images, which we compare to EIT images. We initiate the CME with an out-of-equilibrium flux rope with an orientation and chirality chosen in agreement with observations of a H-alpha filament. During the eruption, one footpoint of the flux rope reconnects with streamer magnetic field lines and with open field lines from the adjacent coronal hole. It yields an eruption which has a mix of closed and open twisted field lines due to interchange reconnection and only one footpoint line-tied to the source region. Even with the large-scale reconnection, we find no evidence of strong rotation of the CME as it propagates. We study the CME deflection and find that the effect of the Lorentz force is a deflection of the CME by about 3 deg/Rsun towards the East during the first 30 minutes of the propagation. We also produce coronagraphic and EUV images of the CME, which we compare with real images, identifying a dimming region associated with the reconnection process. We discuss the implication of our results for the arrival at Earth of CMEs originating from the limb and for models to explain the presence of open field lines in magnetic clouds.Comment: 14 pages, 8 Figures, accepted to Astrophysical Journa

From Hurwitz numbers to Kontsevich-Witten tau-function: a connection by Virasoro operators

In this letter,we present our conjecture on the connection between the Kontsevich--Witten and the Hurwitz tau-functions. The conjectural formula connects these two tau-functions by means of the $GL(\infty)$ group element. An important feature of this group element is its simplicity: this is a group element of the Virasoro subalgebra of $gl(\infty)$. If proved, this conjecture would allow to derive the Virasoro constraints for the Hurwitz tau-function, which remain unknown in spite of existence of several matrix model representations, as well as to give an integrable operator description of the Kontsevich--Witten tau-function.Comment: 13 page

Spin Calogero Particles and Bispectral Solutions of the Matrix KP Hierarchy

Pairs of $n\times n$ matrices whose commutator differ from the identity by a matrix of rank $r$ are used to construct bispectral differential operators with $r\times r$ matrix coefficients satisfying the Lax equations of the Matrix KP hierarchy. Moreover, the bispectral involution on these operators has dynamical significance for the spin Calogero particles system whose phase space such pairs represent. In the case $r=1$, this reproduces well-known results of Wilson and others from the 1990's relating (spinless) Calogero-Moser systems to the bispectrality of (scalar) differential operators. This new class of pairs $(L, \Lambda)$ of bispectral matrix differential operators is different than those previously studied in that $L$ acts from the left, but $\Lambda$ from the right on a common $r\times r$ eigenmatrix.Comment: 16 page