Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge.

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism

Electron Population Aging Models for Wide-Angle Tails

Color-color diagrams have been useful in studying the spectral shapes in radio galaxies. At the workshop we presented color-color diagrams for two wide-angle tails, 1231+674 and 1433+553, and found that the standard aging models do not adequately represent the observed data. Although the JP and KP models can explain some of the observed points in the color-color diagram, they do not account for those found near the power-law line. This difficulty may be attributable to several causes. Spectral tomography has been previously used to discern two separate electron populations in these sources. The combination spectra from two such overlying components can easily resemble a range of power-laws. In addition, any non-uniformity in the magnetic field strength can also create a power-law-like spectrum. We will also discuss the effects that angular resolution has on the shape of the spectrum.Comment: 4 pages, 1 figure, proceedings from 1999 'Life Cycles of Radio Galaxies' workshop at STScI in Baltimore, M

Coaxial Jets and Sheaths in Wide-Angle-Tail Radio Galaxies

We add 20, 6 and 3.6 cm wavelength VLA observations of two WATs, 1231+674 and 1433+553, to existing VLA data at 6 and 20 cm, in order to study the variations of spectral index as a function of position. We apply the spectral tomography process that we introduced in our analysis of 3C67, 3C190 and 3C449. Both spectral tomography and polarization maps indicate that there are two distinct extended components in each source. As in the case of 3C449, we find that each source has a flat spectrum jet surrounded by a steeper spectrum sheath. The steep components tend to be more highly polarized than the flat components. We discuss a number of possibilities for the dynamics of the jet/sheath systems, and the evolution of their relativistic electron populations. While the exact nature of these two coaxial components is still uncertain, their existence requires new models of jets in FR I sources and may also have implications for the dichotomy between FR Is and FR IIs.Comment: 29 text pages plus 13 figures. Scheduled for publication in May 10, 1999 Ap

A Circumbinary Planet in Orbit Around the Short-Period White-Dwarf Eclipsing Binary RR Cae

By using six new determined mid-eclipse times together with those collected from the literature, we found that the Observed-Calculated (O-C) curve of RR Cae shows a cyclic change with a period of 11.9 years and an amplitude of 14.3s, while it undergoes an upward parabolic variation (revealing a long-term period increase at a rate of dP/dt =+4.18(+-0.20)x10^(-12). The cyclic change was analyzed for the light-travel time effect that arises from the gravitational influence of a third companion. The mass of the third body was determined to be M_3*sin i' = 4.2(+-0.4) M_{Jup} suggesting that it is a circumbinary giant planet when its orbital inclination is larger than 17.6 degree. The orbital separation of the circumbinary planet from the central eclipsing binary is about 5.3(+-0.6)AU. The period increase is opposite to the changes caused by angular momentum loss via magnetic braking or/and gravitational radiation, nor can it be explained by the mass transfer between both components because of its detached configuration. These indicate that the observed upward parabolic change is only a part of a long-period (longer than 26.3 years) cyclic variation, which may reveal the presence of another giant circumbinary planet in a wide orbit.Comment: It will be published in the MNRA

X-ray and optical observations of the unique binary system HD49798/RXJ0648.0-4418

We report the results of XMM-Newton observations of HD49798/RXJ0648.0-4418, the only known X-ray binary consisting of a hot sub-dwarf and a white dwarf. The white dwarf rotates very rapidly (P=13.2 s) and has a dynamically measured mass of 1.28+/-0.05 M_sun. Its X-ray emission consists of a strongly pulsed, soft component, well fit by a blackbody with kT~40 eV, accounting for most of the luminosity, and a fainter hard power-law component (photon index ~1.6). A luminosity of ~10^{32} erg/s is produced by accretion onto the white dwarf of the helium-rich matter from the wind of the companion, which is one of the few hot sub-dwarfs showing evidence of mass-loss. A search for optical pulsations at the South African Astronomical Observatory 1.9-m telescope gave negative results. X-rays were detected also during the white dwarf eclipse. This emission, with luminosity 2x10^{30} erg/s, can be attributed to HD 49798 and represents the first detection of a hot sub-dwarf star in the X-ray band. HD49798/RXJ0648.0-4418 is a post-common envelope binary which most likely originated from a pair of stars with masses ~8-10 M_sun. After the current He-burning phase, HD 49798 will expand and reach the Roche-lobe, causing a higher accretion rate onto the white dwarf which can reach the Chandrasekhar limit. Considering the fast spin of the white dwarf, this could lead to the formation of a millisecond pulsar. Alternatively, this system could be a Type Ia supernova progenitor with the appealing characteristic of a short time delay, being the descendent of relatively massive stars.Comment: Accepted for publication on The Astrophysical Journa

First Attempt at Spectroscopic Detection of Gravity Modes in a Long-Period Pulsating Subdwarf B Star -- PG 1627+017

In the first spectroscopic campaign for a PG 1716 variable (or long-period pulsating subdwarf B star), we succeeded in detecting velocity variations due to g-mode pulsations at a level of 1.0-1.5 km/s.The observations were obtained during 40 nights on 2-m class telescopes in Arizona, South Africa,and Australia. The target,PG1627+017, is one of the brightest and largest amplitude stars in its class.It is also the visible component of a post-common envelope binary.Our final radial velocity data set includes 84 hours of time-series spectroscopy over a time baseline of 53 days. Our derived radial velocity amplitude spectrum, after subtracting the orbital motion, shows three potential pulsational modes 3-4 sigma above the mean noise level, at 7201.0s,7014.6s and 7037.3s.Only one of the features is statistically likely to be real,but all three are tantalizingly close to, or a one day alias of, the three strongest periodicities found in the concurrent photometric campaign. We further attempted to detect pulsational variations in the Balmer line amplitudes. The single detected periodicity of 7209 s, although weak, is consistent with theoretical expectations as a function of wavelength.Furthermore, it allows us to rule out a degree index of l= 3 or l= 5 for that mode. Given the extreme weakness of g-mode pulsations in these stars,we conclude that anything beyond simply detecting their presence will require larger telescopes,higher efficiency spectral monitoring over longer time baselines,improved longitude coverage, and increased radial velocity precision.Comment: 39 pages, 9 figures, 4 tables, ApJ accepted. See postscript for full abtrac

Persistence in Cluster--Cluster Aggregation

Persistence is considered in diffusion--limited cluster--cluster aggregation, in one dimension and when the diffusion coefficient of a cluster depends on its size $s$ as $D(s) \sim s^\gamma$. The empty and filled site persistences are defined as the probabilities, that a site has been either empty or covered by a cluster all the time whereas the cluster persistence gives the probability of a cluster to remain intact. The filled site one is nonuniversal. The empty site and cluster persistences are found to be universal, as supported by analytical arguments and simulations. The empty site case decays algebraically with the exponent $\theta_E = 2/(2 - \gamma)$. The cluster persistence is related to the small $s$ behavior of the cluster size distribution and behaves also algebraically for $0 \le \gamma < 2$ while for $\gamma < 0$ the behavior is stretched exponential. In the scaling limit $t \to \infty$ and $K(t) \to \infty$ with $t/K(t)$ fixed the distribution of intervals of size $k$ between persistent regions scales as $n(k;t) = K^{-2} f(k/K)$, where $K(t) \sim t^\theta$ is the average interval size and $f(y) = e^{-y}$. For finite $t$ the scaling is poor for $k \ll t^z$, due to the insufficient separation of the two length scales: the distances between clusters, $t^z$, and that between persistent regions, $t^\theta$. For the size distribution of persistent regions the time and size dependences separate, the latter being independent of the diffusion exponent $\gamma$ but depending on the initial cluster size distribution.Comment: 14 pages, 12 figures, RevTeX, submitted to Phys. Rev.

Cluster persistence in one-dimensional diffusion--limited cluster--cluster aggregation

The persistence probability, $P_C(t)$, of a cluster to remain unaggregated is studied in cluster-cluster aggregation, when the diffusion coefficient of a cluster depends on its size $s$ as $D(s) \sim s^\gamma$. In the mean-field the problem maps to the survival of three annihilating random walkers with time-dependent noise correlations. For $\gamma \ge 0$ the motion of persistent clusters becomes asymptotically irrelevant and the mean-field theory provides a correct description. For $\gamma < 0$ the spatial fluctuations remain relevant and the persistence probability is overestimated by the random walk theory. The decay of persistence determines the small size tail of the cluster size distribution. For $0 < \gamma < 2$ the distribution is flat and, surprisingly, independent of $\gamma$.Comment: 11 pages, 6 figures, RevTeX4, submitted to Phys. Rev.

Fraction of uninfected walkers in the one-dimensional Potts model

The dynamics of the one-dimensional q-state Potts model, in the zero temperature limit, can be formulated through the motion of random walkers which either annihilate (A + A -> 0) or coalesce (A + A -> A) with a q-dependent probability. We consider all of the walkers in this model to be mutually infectious. Whenever two walkers meet, they experience mutual contamination. Walkers which avoid an encounter with another random walker up to time t remain uninfected. The fraction of uninfected walkers is investigated numerically and found to decay algebraically, U(t) \sim t^{-\phi(q)}, with a nontrivial exponent \phi(q). Our study is extended to include the coupled diffusion-limited reaction A+A -> B, B+B -> A in one dimension with equal initial densities of A and B particles. We find that the density of walkers decays in this model as \rho(t) \sim t^{-1/2}. The fraction of sites unvisited by either an A or a B particle is found to obey a power law, P(t) \sim t^{-\theta} with \theta \simeq 1.33. We discuss these exponents within the context of the q-state Potts model and present numerical evidence that the fraction of walkers which remain uninfected decays as U(t) \sim t^{-\phi}, where \phi \simeq 1.13 when infection occurs between like particles only, and \phi \simeq 1.93 when we also include cross-species contamination.Comment: Expanded introduction with more discussion of related wor

Persistence properties of a system of coagulating and annihilating random walkers

We study a d-dimensional system of diffusing particles that on contact either annihilate with probability 1/(q-1) or coagulate with probability (q-2)/(q-1). In 1-dimension, the system models the zero temperature Glauber dynamics of domain walls in the q-state Potts model. We calculate P(m,t), the probability that a randomly chosen lattice site contains a particle whose ancestors have undergone exactly (m-1) coagulations. Using perturbative renormalization group analysis for d < 2, we show that, if the number of coagulations m is much less than the typical number M(t), then P(m,t) ~ m^(z/d) t^(-theta), with theta=d Q + Q(Q-1/2) epsilon + O(epsilon^2), z=(2Q-1) epsilon + (2 Q-1) (Q-1)(1/2+A Q) epsilon^2 +O(epsilon^3), where Q=(q-1)/q, epsilon =2-d and A =-0.006. M(t) is shown to scale as t^(d/2-delta), where delta = d (1 -Q)+(Q-1)(Q-1/2) epsilon+ O(epsilon^2). In two dimensions, we show that P(m,t) ~ ln(t)^(Q(3-2Q)) ln(m)^((2Q-1)^2) t^(-2Q) for m << t^(2 Q-1). The 1-dimensional results corresponding to epsilon=1 are compared with results from Monte Carlo simulations.Comment: 12 pages, revtex, 5 figure