Seven coordinate molybdenum and tungsten complexes containing Tpm and Tpm derivatives and the impact of ligand substitution on NMR chemical shifts

A series of known and new seven coordinate molybdenum and tungsten complexes of tris(pyrazolyl)methane (Tpm) and substituted Tpm, [TpmM(CO)3X]+, have been synthesized. Depending on the identity of X, (bromo, iodo, hydrido) and the substitution of the Tpm ligand, substantial chemical shift differences are observed for the hydrogen on the central carbon of the Tpm ligand. Factors impacting the chemical shift of the hydrogen on the central carbon of the Tpm ligand, such as the electron donating ability of the Tpm ligand and the electronegativity of the additional ligand on the metal, will be discussed

The relative influence of above and below ground competition on the growth and survival of ryegrass seedlings transplanted into a hill country pasture : a thesis presented in partial fulfilment of the requirements for the degree of Master of Agricultural Science in Plant Science at Massey University

In many pasture improvement programmes, for example oversowing in hill country, seedling survival is influenced by competition from the existing vegetation. Competition between pasture plants occurs when resources are limited and may be for factors above or below ground, or both. Technically, the effective separation of above and below ground competition is difficult and considerable problems have been associated with previous studies. A technique developed for field studies combined the treatments of clipping herbage surrounding the transplanted seedling to prevent above ground competition and inserting a metal cylinder (root tube) into the ground to prevent below ground competition, resulting in conditions of shoot, root, full or no competition. Ryegrass seedlings were transplanted in August 1986 into a pasture in summer dry hill country near Wanganui and subjected to shoot, root, full or no competition from the existing vegetation. The duration of the experiment was three months. The effect of competition on the growth of the ryegrass seedlings was assessed by non destructive measurements (plant height, tiller number) taken at approximately weekly intervals. On three occasions, destructive harvests were made and the dry weight of shoots and roots was recorded. Below ground competition occurred before, and was more severe than above ground competition, as exemplified by changes in plant size. Ryegrass plants in the treatments with below ground competition were 80 % lighter, 64 % smaller and had 60 % fewer tillers than plants with either shoot competition or no competition. The distribution of plant size was highly skewed, and indicated that the stress plants encountered when subjected to below ground competition was severe. The effect of above ground competition on ryegrass growth was small except when root competition was also present. Shaded plants were usually taller than those that were unshaded. In conclusion, below ground competition, possibly for soil nutrients, was shown to be the major influence on growth and development of transplanted seedlings at the hill country site studied. The survival of seedlings introduced into pasture was also dependent on environmental factors, especially soil moisture, and therefore important in summer dry hill country. In a second experiment during spring 1986, ryegrass seedlings were grown in tubes and transplanted into a hill pasture at Wanganui. The six treatments consisted of combinations of two planting dates, two tube lengths, two harvest dates and were arranged as a randomised complete block design Seedling survival was high over all treatments (98 %), probably because rainfall during the experimental period was high

Atmospheric Retrieval for Super-Earths: Uniquely Constraining the Atmospheric Composition with Transmission Spectroscopy

We present a retrieval method based on Bayesian analysis to infer the atmospheric compositions and surface or cloud-top pressures from transmission spectra of exoplanets with general compositions. In this study, we identify what can unambiguously be determined about the atmospheres of exoplanets from their transmission spectra by applying the retrieval method to synthetic observations of the super-Earth GJ 1214b. Our approach to infer constraints on atmospheric parameters is to compute their joint and marginal posterior probability distributions using the MCMC technique in a parallel tempering scheme. A new atmospheric parameterization is introduced that is applicable to general atmospheres in which the main constituent is not known a priori and clouds may be present. Our main finding is that a unique constraint of the mixing ratios of the absorbers and up to two spectrally inactive gases (such as N2 and primordial H2+He) is possible if the observations are sufficient to quantify both (1) the broadband transit depths in at least one absorption feature for each absorber and (2) the slope and strength of the molecular Rayleigh scattering signature. The surface or cloud-top pressure can be quantified if a surface or cloud deck is present. The mean molecular mass can be constrained from the Rayleigh slope or the shapes of absorption features, thus enabling to distinguish between cloudy hydrogen-rich atmospheres and high mean molecular mass atmospheres. We conclude, however, that without the signature of Rayleigh scattering--even with robustly detected infrared absorption features--there is no reliable way to tell if the absorber is the main constituent of the atmosphere or just a minor species with a mixing ratio of <0.1%. The retrieval method leads us to a conceptual picture of which details in transmission spectra are essential for unique characterizations of well-mixed atmospheres.Comment: 23 pages, 13 figures, accepted at ApJ, submitted to ApJ on Nov 4, 201

Photochemistry in Terrestrial Exoplanet Atmospheres III: Photochemistry and Thermochemistry in Thick Atmospheres on Super Earths and Mini Neptunes

Some super Earths and mini Neptunes will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO2 rather than CH4 or CO in a H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons (C2H2 and C2H4). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b like planets we find that (1) C2H2 features at 1.0 and 1.5 micron in transmission and C2H2 and C2H4 features at 9-14 micron in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.Comment: Accepted for publication on Ap

A Temperature and Abundance Retrieval Method for Exoplanet Atmospheres

We present a new method to retrieve molecular abundances and temperature profiles from exoplanet atmosphere photometry and spectroscopy. We run millions of 1D atmosphere models in order to cover the large range of allowed parameter space, and present error contours in the atmospheric properties, given the data. In order to run such a large number of models, we have developed a parametric pressure-temperature (P-T) profile coupled with line-by-line radiative transfer, hydrostatic equilibrium, and energy balance, along with prescriptions for non-equilibrium molecular composition and energy redistribution. We apply our temperature and abundance retrieval method to the atmospheres of two transiting exoplanets, HD 189733b and HD 209458b, which have the best available Spitzer and HST observations. For HD 189733b, we find efficient day-night redistribution of energy in the atmosphere, and molecular abundance constraints confirming the presence of H2O, CO, CH4, and CO2. For HD 209458b, we confirm and constrain the day-side thermal inversion in an average 1D temperature profile. We also report independent detections of H$_2$O, CO, CH$_4$ and CO$_2$ on the dayside of HD 209458b, based on six-channel Spitzer photometry. We report constraints for HD 189733b due to individual data sets separately; a few key observations are variable in different data sets at similar wavelengths. Moreover, a noticeably strong carbon dioxide absorption in one data set is significantly weaker in another. We must, therefore, acknowledge the strong possibility that the atmosphere is variable, both in its energy redistribution state and in the chemical abundances.Comment: 20 pages in emulateapj format, 11 figures. Final version, after proof correction

Thermal Emission from Transiting Very-Hot Jupiters: Prospects for Ground-based Detection at Optical Wavelengths

Very hot Jupiters (VHJs) are defined as Jupiter-mass extrasolar planets with orbital periods shorter than three days. For low albedos the effective temperatures of irradiated VHJs can reach 2500-3000 K. Thermal emission from VHJs is therefore potentially strong at optical wavelengths. We explore the prospects of detecting optical-wavelength thermal emission during secondary eclipse with existing ground-based telescopes. We show that OGLE-TR-56b and OGLE-TR-132b are the best suited candidates for detection, and that the prospects are highest around z'-band (~0.9 microns). We also speculate that any newly discovered VHJs with the right combination of orbital separation and host star parameters could be thermally detected in the optical. The lack of detections would still provide constraints on the planetary albedos and re-radiation factors.Comment: accepted for publication on ApJ

A Framework for Quantifying the Degeneracies of Exoplanet Interior Compositions

Several transiting super-Earths are expected to be discovered in the coming few years. While tools to model the interior structure of transiting planets exist, inferences about the composition are fraught with ambiguities. We present a framework to quantify how much we can robustly infer about super-Earth and Neptune-size exoplanet interiors from radius and mass measurements. We introduce quaternary diagrams to illustrate the range of possible interior compositions for planets with four layers (iron core, silicate mantles, water layers, and H/He envelopes). We apply our model to CoRoT-7b, GJ 436b, and HAT-P-11b. Interpretation of planets with H/He envelopes is limited by the model uncertainty in the interior temperature, while for CoRoT-7b observational uncertainties dominate. We further find that our planet interior model sharpens the observational constraints on CoRoT-7b's mass and radius, assuming the planet does not contain significant amounts of water or gas. We show that the strength of the limits that can be placed on a super-Earth's composition depends on the planet's density; for similar observational uncertainties, high-density super-Mercuries allow the tightest composition constraints. Finally, we describe how techniques from Bayesian statistics can be used to take into account in a formal way the combined contributions of both theoretical and observational uncertainties to ambiguities in a planet's interior composition. On the whole, with only a mass and radius measurement an exact interior composition cannot be inferred for an exoplanet because the problem is highly underconstrained. Detailed quantitative ranges of plausible compositions, however, can be found.Comment: 20 pages, 10 figures, published in Ap