Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series

Continuous phase amplification with a Sagnac interferometer

We describe a weak value inspired phase amplification technique in a Sagnac interferometer. We monitor the relative phase between two paths of a slightly misaligned interferometer by measuring the average position of a split-Gaussian mode in the dark port. Although we monitor only the dark port, we show that the signal varies linearly with phase and that we can obtain similar sensitivity to balanced homodyne detection. We derive the source of the amplification both with classical wave optics and as an inverse weak value.Comment: 5 pages, 4 figures, previously submitted for publicatio

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An-O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+

Ultrasensitive Beam Deflection Measurement via Interferometric Weak Value Amplification

We report on the use of an interferometric weak value technique to amplify very small transverse deflections of an optical beam. By entangling the beam's transverse degrees of freedom with the which-path states of a Sagnac interferometer, it is possible to realize an optical amplifier for polarization independent deflections. The theory for the interferometric weak value amplification method is presented along with the experimental results, which are in good agreement. Of particular interest, we measured the angular deflection of a mirror down to 560 femtoradians and the linear travel of a piezo actuator down to 20 femtometers

Precision frequency measurements with interferometric weak values

We demonstrate an experiment which utilizes a Sagnac interferometer to measure a change in optical frequency of 129 kHz per root Hz with only 2 mW of continuous wave, single mode input power. We describe the measurement of a weak value and show how even higher frequency sensitivities may be obtained over a bandwidth of several nanometers. This technique has many possible applications, such as precision relative frequency measurements and laser locking without the use of atomic lines.Comment: 4 pages, 3 figures, published in PR

Optimizing the Signal to Noise Ratio of a Beam Deflection Measurement with Interferometric Weak Values

The amplification obtained using weak values is quantified through a detailed investigation of the signal to noise ratio for an optical beam deflection measurement. We show that for a given deflection, input power and beam radius, the use of interferometric weak values allows one to obtain the optimum signal to noise ratio using a coherent beam. This method has the advantage of reduced technical noise and allows for the use of detectors with a low saturation intensity. We report on an experiment which improves the signal to noise ratio for a beam deflection measurement by a factor of 54 when compared to a measurement using the same beam size and a quantum limited detector

Interferometric weak value deflections: quantum and classical treatments

We derive the weak value deflection given in a paper by Dixon et al. (Phys. Rev. Lett. 102, 173601 (2009)) both quantum mechanically and classically. This paper is meant to cover some of the mathematical details omitted in that paper owing to space constraints

Testing Gravity in the Outer Solar System: Results from Trans-Neptunian Objects

The inverse square law of gravity is poorly probed by experimental tests at distances of ~ 10 AUs. Recent analysis of the trajectory of the Pioneer 10 and 11 spacecraft have shown an unmodeled acceleration directed toward the Sun which was not explained by any obvious spacecraft systematics, and occurred when at distances greater than 20 AUs from the Sun. If this acceleration represents a departure from Newtonian gravity or is indicative of an additional mass distribution in the outer solar system, it should be detectable in the orbits of Trans-Neptunian Objects (TNOs). To place limits on deviations from Newtonian gravity, we have selected a well observed sample of TNOs found orbiting between 20 and 100 AU from the Sun. By examining their orbits with modified orbital fitting software, we place tight limits on the perturbations of gravity that could exist in this region of the solar system.Comment: 20 pages, 4 figures, 2 tables, uses AASTex v5.x macro

How Well Do We Know the Orbits of the Outer Planets?

This paper deals with the problem of astrometric determination of the orbital elements of the outer planets, in particular by assessing the ability of astrometric observations to detect perturbations of the sort expected from the Pioneer effect or other small perturbations to gravity. We also show that while using simplified models of the dynamics can lead to some insights, one must be careful to not over-simplify the issues involved lest one be misled by the analysis onto false paths. Specifically, we show that the current ephemeris of Pluto does not preclude the existence of the Pioneer effect. We show that the orbit of Pluto is simply not well enough characterized at present to make such an assertion. A number of misunderstandings related to these topics have now propagated through the literature and have been used as a basis for drawing conclusions about the dynamics of the solar system. Thus, the objective of this paper is to address these issues. Finally, we offer some comments dealing with the complex topic of model selection and comparison.Comment: Accepted for publication in the Ap